Class student dicussions answers Assignment Example | Topics and Well Written Essays - 500 words - 2

Class student dicussions answers - Assignment Example You also provided a simple ‘what to do’ measures in order to eliminate the risk of viruses affecting the computer. It is a good insight that you gave about training the new users on how to detect scam emails and not click on the provided unknown links, and also executing an anti-malware or anti-virus scan whenever accessing an external memory drive. You could have also added not auto-executing flash drive programs or executables. Another thing that I feel should be a part of training for novices should be proper usage of trusted sites for downloads security features available in the browsers. Brain, you defined what Kevin said. You explained how a honeypot is implemented outside the main network and it sacrifices itself for the protection of the main, critical network. The best things that you told about the honeypot networks in general, are the disadvantages of implementing them. Cost was always a default factor but yes it would take more toil on the system administrator to monitor and look after this network’s resources. I would partially agree with the last comment you made on comparing advantages and disadvantages. For critical data organizations, we do need these honeypots but for smaller organizations, we cannot afford to have such a high cost. You also specifically mentioned what intrusion detection systems and firewalls we can use for information security. As opposed to Kevin, you have provided specific details on three main techniques of ensuring information security within the organization. You also made good points on differentiating how software and hardware security systems work in unison to provide maximum security to the organizational data. I completely agree that software based security is either algorithmic or rule based but hardware based security is almost rule based. The explanation of how routers work

Purpose and Effects of Section 4 of Human Rights Act Assignment

Purpose and Effects of Section 4 of Human Rights Act - Assignment Example In the case of primary laws, the right simply accrues upon a finding of incompatibility but in the case of secondary laws, there must be a determination of incompatibility in addition to the requirement that the primary legislation relevant to it prevents its removal. Instances, when the courts used this prerogative, is in the cases of International Transport Roth GMBH and others v Secretary of State for the Home Department and the R (H) v Mental Health Review Tribunal N&E London Region.  In Roth, a group of lorry drivers and haulage companies challenged Part II of the Immigration and Asylum Act for being incompatible with convention rights. The said legislation was passed to answer the flagrant clandestine illegal entry by penalizing, among others, the owner, driver, operator, and hirer with a fine of  £2000. The lower court declared the said provisions of law incompatible with Art 6 of the HRA because it penalizes, in effect, a criminal act despite its claim to the contrary and therefore violates Art 6 because the determination of guilt, among others, is single left to the Secretary of State and Art 1 because of the penalty of vehicle detention involved infringement on property rights. On the other hand, in the R(H) case, the court made a determination of incompatibility against s 73 of the Mental Health Act of 1983 on the ground that it violates Art 5 on the Right to Life and Liberty by placing the burden of proof on the applicant rather than the hospital in showing basis for detention of patient in a mental hospital.  As stated, only certain courts enumerated by s 4 can exercise this prerogative. However, the preceding section of the HRA which requires that both primary and secondary legislation â€Å"must be read and given effect in a way which is compatible with Convention rights† does not distinguish which courts are obliged or not. The implication is that although not all courts are given the prerogative to declare incompatibility with conv ention rights, all courts must nevertheless take into consideration the issue of compatibility but apply the national law just the same. The remedy in such cases is an appeal to a higher court with the power to declare such incompatibility.

Generalized anxiety disorder Essay Example | Topics and Well Written Essays - 750 words

Generalized anxiety disorder - Essay Example Prior to the conclusion, the researcher will provide some recommendations on how a person could avoid experiencing GAD. A generalized anxiety disorder is normally characterized with chronic anxiety or exaggerated worry or tension. (Haines, 2005) In the process, people who are going through GAD are normally restless, easily fatigue and irritable. (Medscape Medical News, 2003) In fact, most of these patients often expect serious problems to happen with regards to their health, money, family life including their work or school activities and performance. The problem with GAD is that patients are unable to control the degree of their worrying. In most cases, extreme worrying, fear and anxiety significantly affect the normal functioning of their everyday life. months. (Robins and Regier, 1991) Several studies also reveal that GAD can be triggered by a person’s genes (Kendler et al., 1992) or the abnormal level of neurotransmitters in the brain. (Stephens, 2005) Environmental factors such as the death of a loved one, divorce cases, losing or changing jobs or schools and any other traumatic and stressful situations like physical, mental or emotional abuse could trigger the presence of GAD. People who are suspected to experience GAD are normally diagnosed through questioning of their medical history combined with physical examination. (Haines, 2005) Basically, there is not laboratory test that could diagnose GAD. Instead, physicians normally base their diagnosis by looking for any signs of physical illness and the causes, duration, and seriousness of these symptoms. Among the common symtoms of GAD includes stiff muscle, inability to relax, irritability, insomia and other physical symtoms like fatigue, trembling, muscle tension, headache and irritability. (Stephens, 2005) GAD is commonly treated either through proper medication particularly the benzodiazepines or tranquilizers such as Valium, Ativan, Librium and Xanax. Other pharmacological drugs

The use of IFI replacing PRSP Essay Example | Topics and Well Written Essays - 1750 words

The use of IFI replacing PRSP - Essay Example It is a road map that leads the organizations involved in this process, to the making of the final PRSP. During the period in which the document is formulated, greater participation by the civil society is encouraged. The data that provides information on the nature of poverty and its distribution are collected and considered for statistical analysis. According to the IMF and the World Bank, the PRSP document must present an exclusive description of the participatory process for the making of the document, a comprehensive diagnosis of the problem of poverty, clear description of the social and economic priorities and transparent targets in accordance with the costs incurred by the society. The PRSP acts as an indicator of the monitoring system and helps in evaluating the process of progress (Christiansen and Hovland, â€Å"The PRSP Initiative: Multilateral Policy Change and the Role of Research†). ... This is because the process is highly context specific and the does not follow any pre determined critical pathway that would directly lead the government of the country to develop the PRSP (Christiansen and Hovland, â€Å"The PRSP Initiative: Multilateral Policy Change and the Role of Research†). The basic principle followed for the drafting of the interim PRSP is to follow the broad participation rate, engagement of the civil society as well as the private sector in deciding the structure of the expenditure and their priorities. Structural adjustment measures in Pakistan Pakistan has undergone a number of structural adjustment programs since the 1970s. The adjustment modification that was undertaken in the 1980s had brought improvement in the economic performance of the country and also made the common population capable of responding to the economic changes occurring in the economy of Pakistan. However, the focus of these structural adjustment lied solely on increasing effi ciency of economic activities in order to bring economic benefits, but, attention had not been given to the problem of rising income inequality. Incidence of poverty has grown over the years and at present there is huge inequality in distribution of income (James and Pyatt, â€Å"Three-Gap Analysis of Structural Adjustment in Pakistan†). These factors have necessitated the drafting of the Poverty Reduction Strategy Papers. The government (Finance Ministry of the Government) along with the civic bodies in the nation, individual participants and non-governmental organizations work in synchronization to develop the draft of the PRSP backed by the international financial institutions (IFI). The PRSP has been aimed at replacing the existing structural adjustment measures in the

Moments of dramatic tension Essay Example for Free

Moments of dramatic tension Essay Choose two scenes which you consider to be particularly interesting moments of dramatic tension. Write about why they are especially dramatic and why they are important in the play  For this essay I am going to concentrate on the scene at the end of act one in A View from the Bridge by Arthur Miller. In the previous scene Eddie, the main character, has just been to see Alfieri, a lawyer who once represented Eddies father and also the narrator for this play, for legal and moral advice on what to do. Eddie is confused and needs someone to kick him in the right direction. I know this because Alfieri said that his eyes looked like tunnels. Eddie feels that Rodolfo is gay and is only after his passport. Another reason Eddie is confused is that he loves Catherine too much. Alfieri has just told Eddie that there is nothing that Eddie can do apart from go to the Immigration Bureau or accept the situation and be happy for the two. This leads into this essays scene. It is set in the apartment and opens with Catherine talking about Marco and Rodolfos trip to Africa. I believe that the tension begins to grow when Eddie dismisses her excitement. I think this because I believe Eddie is trying to not think about Rodolfo so is saying so what if they have. It is obvious that Eddie really is interested when he says How long that take you, Marco. Eddie is directing this conversation at Marco and has taken Rodolfo out of the conversation. This shows that Eddie does not like Rodolfo and would rather not think of him. The conversation then carries awhile the tension decreases and the entire family is now into the conversation. Eddie then belittles Beatrice in front of everyone. Beatrice never knew that sardines could not be caught with a hook. I think that this the tension increases with this. Eddie and Beatrices relationship has not been smooth lately and this didnt help.  To release the tension Eddie comes up with a joke. He says that oranges are green and are painted to give them colour. Rodolfo then belittles Eddie by saying pointing out the obvious and saying that lemons are green. I believe he did this because the one of the themes of the book is family loyalty and I think he said this to get revenge for Beatrice. This causes the tension to develop more. Eddie does not want to even talk to Rodolfo let alone be disrespected by him. The tension is then released by Beatrice who changes the topic. This conversation too caries on for sometime and Eddie makes another joke. Eddie says they count the kids and theres a couple extra than when they left? Rodolfo then says that it is stricter in Italy than it is in Brooklyn. Eddie gets offended by this because Rodolfo is saying that American girls (e.g. Catherine) are easier. I believe that the dramatic tension at this point is higher than any part before it. Miller shows the tension by writing stage directions for Eddie to rise and pace up and down. There is then a conversation between Eddie and Rodolfo. Eddie is comparing Rodolfo and Catherines relationship to how one would be in their town in Italy. Beatrice takes Rodolfos side in this argument as she knows where it is going. Marco takes Eddies side as he doesnt want any trouble. Marco also tells Rodolfo off and it is clear that Marco wants this argument to end. An argument begins between Beatrice and Eddie then. They are arguing whether a person is safer during the day or at night . The tension is still on high alert when Catherine asks Rodolfo to dance deliberately to annoy Eddie and show him that nothing will come between the twos relationship. Rodolfo decides not to as he knows that he has already pushed Eddie enough but eventually gives in.  Once again Beatrice lowers the tension by changing the topic. The focus goes back to fishing and it is soon revealed that Rodolfo can cook. Once Eddie hears about it he talks and implies Rodolfos homosexuality but Rodolfo takes it as a compliment. Catherine says that he could get a lot of money with these skills and Eddie agrees with her. Eddie says that if he had the skills he would be no where near the waterfront. The tension is rising again as Miller then wrote that Eddie was unconsciously twisting the newspaper. Everyone knows what he is doing so he carries on the speech. While he is talking the newspaper rips in half. I think that this gets everyone nervous and the scene gets more tense. I believe that it signified Eddie getting an idea in his head, like a light bulb above someone on TV when they get an idea. He asks Marco if he wants to go to see a fight next week. He also asks Rodolfo trying to see his reaction. Boxing is a masculine sport and he thought he was asking a woman. Catherine believes that Eddie is being nice now so she goes to get some coffee. At this point of the scene I think that it is not as tense as it just was but I think that everyone is still nervous. Eddie and Rodolfo then begin to spar and I believe that the audience are now at the edge of their seats waiting to see what will happen. Everyone is impressed thinking that Eddie is making the effort to try to like Rodolfo, but then Eddie comes with a trick attack and lands a blow on Rodolfo. It then becomes clear what Eddies intensions were, he wanted an excuse to take his anger on Rodolfo out. Rodolfo does not want to make anything worse so he says that it didnt hurl him and only surprised him. The tension once again is high and Rodolfo asks Catherine to dance to annoy Eddie. He is saying that nothing will get between Catherine and his relationship. Marco then comes and sits a chair in front of Eddie. He challenges him to lift to it from the bottom with one hand. Eddie thinks that this will be easy but soon finds out that it isnt when he fails. Marco then lifts it above his head to show that he is stronger. Until now Marco had always been on his side by apologising for his brother, Rodolfo, but Eddie has now lost his only supporter. The tension rises as they stare at each other and Marco smiles. Another thing that adds tension here is the stage directions. They say that Marco held the chair like a weapon. This creates tension as it shows that Marco is threatening Eddie. The scene finished with the tension very high and with Eddie physically threatened. In this scene Arthur Miller has used many ways to show the tension rising. One of these was writing the stage directions. This creates visual images which are really important as they stress the tension; it shows the reader what the audience sees and also shows the tension. Another way he showed the tension was by making the sentences longer. This slows down the pace of the play and created tension. Another way he shows tension is by adding pauses. These add silence and make the audience/reader want to know what happens next. It also gives a moment for the tension to rise.

Social Policy Essays Social Policy For Sex Offenders

Social Policy Essays Social Policy For Sex Offenders Social Policy For Sex Offenders Children’s protection and safety has become a prominent legislative issue of the 90s and for the millennium. It appears that more and more legislation will continue to be introduced and passed for the best interest of children. The goal is to stop crime against our children in this generation, but for some children it is too late: Anthony Martinez, Polly Klaas, Megan Kanga, the children we did not read about and, unfortunately, those we will be reading about. This paper will discuss Megan’s law (See Appendix A), which requires the registration and notification to communities of released sex offenders. Child abuse legislation proved to be an agenda leader for two other sets of issues: those relating to child care and those relating to personal violence. Child abuse, especially sexual, has infused parents and communities with renewed moral outrage and provided intellectual and political connections to long-standing issues, such as child safety and protection. But perhaps more interestingly, crime legislation gave legitimacy and currency to the consideration of the allied issues of violence, autonomy, and physical safety, including the sexual abuse of children, domestic violence and rape ( Nelson, 1984). Get help with your essay from our expert essay writers Bierker (1989) defined sexual abuse as a sexual activity perpetrated on a child by an older person through coercion. The child lacks the emotional and physical maturity to resist what amounts to abuse of the older person’s position of authority and power. Abuse, by definition, causes pain to the child at the time of the abuse and, unless the abuse is disclosed and dealt with, later in his or her life. In recent high profile cases, the children all appeared to have been sexually abused before they were murdered. Sexual abuse of a child generally moves through increasingly intimate activity. Perpetrators carefully plan not only the abuse, but also arrange for a private place to do it. Parents often give the perpetrator access to their child unwittingly. For example, they may allow their child to engage in group activities which are lead by an unknown perpetrator. Megan’s Law seeks to identify known pedophiles and allow parents to inform and teach their children to avoid these offenders. Sexual offenders are a large and growing part of the prison population. In 1980 state prisons held 20, 500 sex offenders; in 1990 there were 63,600; and in 1994 their were 88, 100. They grew not only in number, but also as a percentage of an expanding state prison population: 6.9 percent of 295,819 inmates in 1980; 9.7 percent of 906, 112 in 1994. In 1991, at least 20 percent of the adult prison population in ten states were sex offenders. Community in-patient and out-patient programs specializing in treating sex offenders have proliferated. Still, it appears that relatively few incarcerated sex offenders actually receive treatment. There is insufficient research to establish consistent estimates of recidivism or to identify effective treatments ( Department of Justice, statistics, 1996). The current climate is severely punitive. Many citizens’ approach is to lock-up all the criminals and never release them. The public seems determined to prevent these individuals from committing new crimes no matter the cost. As a result, by August, 1995, 43 states had enacted statutes requiring offenders to register with a central agency or with a law enforcement agency located in the community into which they are released. In late July 1994, seven-year-old Megan Kanka was raped and strangled to death. Such tragedies are periodically reported in our daily periodical across the country, but the difference here was that Megan’s killer lived across the street from the Kanka family in Hamilton Township, New Jersey. Further, the neighbor had served time in Avenel, a facility for sex offenders in New Jersey. The man had been convicted of molesting children twice previously, but the community knew nothing of his background. Megan’s parents and neighbors learned of Jesse Timmendequa’s history only after he was arrested on July 30, 1994, and had confessed to the murder. Megan’s parents, Richard and Maureen Kanka, and their neighbors organized and angrily confronted their city council as to why they were not informed as to the establishment of this â€Å"house for sex offenders† in their family-oriented community. They demanded that the laws be changed so as allow communities to protect themselves from released sex offenders. Jansson defines policy practice as â€Å"efforts to influence the development, enactment, implementation, or assessment of social policies† through the utilization of policy practice skills (which he identifies as analytic, political, interactional, and value-clarification), and the performance of policy practice tasks (setting agendas, defining problems, making proposals, enacting policy, implementing policy, and assessing policy) (Jansson, 1994). With the fall elections approaching, and several Republican anti-crime initiatives stalled in the Senate, Republicans pushed four bills through the House on May 7, 1995 to crack down on sex offenders, witness tampering, stalkers and those who prey on children and the elderly. The Senate cleared the bill (HR 2137) on sex offenders by voice vote May 9, 1995, and President Clinton signed the bill into law. Republicans were hoping that the bills, which dealt with relatively small issues, would resonate with the public and help their party in November. They spotlighted members that were facing tough reelection campaigns as sponsors of three bills. The sexual offender bill was sponsored by Dick Zimmer, Republican from New Jersey, who was in a tight race for the senate seat being vacated by Bill Bradley. The House debate began on an emotional note, and members quickly passed legislation that would require states and localities to inform communities when dangerous sexual offenders were released from prison. The vote was 418-0 . (See Appendix B). The 1994 crime bill (Pub. L 103-322) requires sex offenders to register their address with local police, and it allows this information to be publicized to preserve safety. The House bill sought to make release of this information mandatory. States that did not comply could lose part of their federal crime fighting funds. The bill also would change a section of the crime law that required states to classify as private all information collected when registering sexual offenders. The bill would allow each state to determine what information is private and what is public (Congressional Quarterly, May 11, 1996). President Clinton strongly supported the bills respecting crimes against children and the elderly. On May 17, 1996, he signed Megan’s Law. He has been an advocate for children since he was governor of Arkansas. The following is an except from the ceremony that took at the White House: â€Å"This has been a week in which our country is moving to combat crime and violence. A couple of days ago we awarded over 9, 000 new police officers to some 2,500 communities. That brings us to 43,000 police officers in 20 months along the road to our goal of 100,000. We’re ahead of schedule and under budget.† â€Å"But today, the valiant presence of five American parents reminds us that this fight against crime is so much more a fight for peace and for safety for our people and especially for our children.† â€Å"I thank the Congress for passing it. I thank those who led the fight. And I thank these families more than anything else. God Bless you all.† (See Appendix C). The Jacob Wetterling Crimes against Children and Sexually Violent Offender Registration Act provides a financial incentive for states to establish effective registration systems for released child molesters and other sexually violent offenders. States that fail to establish conforming registration systems will be subjected to a 10 percent reduction of formula Byrne Grant funding, and resulting surplus funds will be reallocated to states that are in compliance. Unlike Megan’s Law, the Jacob Wetterling Act permitted, but did not require, states to release registration information to the extent necessary to protect the public. In California, state legislation implementing Megan’s Law was passed in September of 1996 (AB 1562 ). The California Department of Justice issued policy and training procedures for local law enforcement agencies directing implementation of Megan’s Law beginning in July, 1997. As of July, 1997, any citizen can request from their local law enforcement agency, a CD ROM containing information, including photographs, of sexual offenders released into the local community. Police and parole agents will be required to notify the community of sexual offenders residing in the neighborhood. In California, Governor Wilson has attempted to go further still, proposing that sex offenders be required to register for life. The rationale underlying such laws is simple: identify all convicted and released sexual offenders, and the community will be able to take action to protect themselves. Notification, according to some, â€Å"could prevent some tragedies from happening again.† Notification is also expected to improve public safety because the public will be able to identify and report risky behavior by sex offenders (e.g. conversing with children, buying sex-oriented magazines) that might escalate into criminal behavior if ignored. The effectiveness of notification probably depends to a considerable degree on the provisions of the state statute, the resources that states and localities are able and willing to provide for implementing the statute, and the dedication and expertise of probation officers, police officers and prosecutors. Notification is most likely to be effective if it is accompanied by extensive community education and carried out by specialist. ( Finn, 1997) Agenda setting stage. Laws regarding sexual abuse came into being in the late 1970s as professionals and the public became aware of the prevalence of this form of child abuse. Since that time, the legal framework has developed dramatically in response to vicious crimes against children. Perhaps no type of crime has received more attention in recent years than crimes against children involving sexual acts and violence. Several recent tragic cases have focused public attention on this type of crime and resulted in public demand that government take stronger action against those who commit those crimes. Specifically, it was the murder of a little girl at the hands of this â€Å"unidentified† sex offender that served the purpose of getting legislators’ and the public’s attention. A victim of sexual abuse himself, Mark J. Welsh argued that identifying offenders would protect children and help prevent molesters from abusing again. Further, he argued that molesters would be recognized everywhere they went, and no one would allow them to be near children. There was no real opposition to this argument— the laws had to be changed. Another important component of the agenda setting stage is the political demand exerted by large voting constituencies and lobbyists. Children do not vote, but parents, relatives, teachers, grass roots organizations, the Child Welfare League of America, and others do strongly represent them in the political arena. In the case of Megan’s Law, support was bipartisan and unanimous. Further, Congress passed Title VII of the Violent Crime Control and Law Enforcement Act of 1994 (Public Law 103-322). That law, entitled the â€Å"Jacob Wetterling Crimes Against Children and Sexually Violent Offender Registration Act,† encouraged states to establish a system where every person who commits a sexual or kidnapping crime against children or who commits sexually violent crime against any person (whether adult or child) would be required to register his address upon release from prison. As further protection, the 1994 Act required states to allow law enforcement agencies to release à ¢â‚¬Å"relevant information† about an offender as necessary to protect the public (Columbia Law, 1995). This community notification provision has been the subject of considerable controversy. Megan’s Law has been challenged by civil libertarians as a violation of sex offenders’ constitutional rights. However, Megan’s Law has thus far survived court challenges. Yet, this has not stopped the American Civil Liberties Union (ACLU), a legal organization dedicated to defending the Constitution, from attacking the constitutionality of notification requirements. The ACLU and others argue that it is unconstitutional to treat sex offenders differently from other violent criminals. Further, the ACLU argues, most sex offenses are committed by people we are not aware are dangerous: friends and relatives and others we do not know about. Community notification tends to generate hysteria about a small group of people for a short period of time. It does not solve the problem, it merely moves ex-offenders around as they are driven from community to community. Moreover, although the ostensible purpose of notification is to permit citizens to take precautions to protect themselves, these laws tend to encourage a state of anxiety which is not helpful to rationally addressing the issue. They also tend to encourage vigilantism. In Washington state, a a released child molester, who had presumedly paid his debt to society, was himself a victim of death threats, assaults and the burning of his home by enraged residents who took the law into their own hands (ACLU, press release, August, 19, 1994). In addition, critics aruge, this law often treats gay men as child molesters and rapists. Years ago, gay men were routinely arrested on felony lewd conduct charges. These were people who were basically engaging in consensual sex with other adults. Although Megan’s Law ostensibly targets sexual predators, the gay community fears that persons arrested for being gay will be identified as sex offenders. Problem defining stage. The problem is whether all released sex offenders should register or not. Different states have relied on different methods of developing notification criteria and as a result, have come up with different criteria. The focus is on developing guidelines for classifying offenders according to the risk they present (low, moderate, high). States have adopted varying criteria to be employed in this classification process. These include the seriousness of the offense, offense history, characteristics of the offender and community support. Proposal writing stage. The bill was included as a special provision in the Federal Violent Crime Control and Law Enforcement Act of 1994 (the â€Å"Act†). At the time it was probably written from an ecological perspective due to Megan’s brutal death and the elections. The bill does potentially â€Å"sweep up† too many people. Policy enacting stage. Congressmen Zimmer and the Republican party seized upon Megan’s death to raise an issue during an election year that no one could possibly oppose: protecting neighborhoods from persons likely to commit heinous sexual crimes. Such conditions encourage politicians to introduce bills that are supported by little, if any, responsible research. In my research for this paper, I spoke to Mr. Greg O’Gorman, an aide to Senator Feinstein. He confirmed the obvious: no politician would oppose Megan’s Law because no one wanted to be identified with sexual offenders. Furthermore, he reported that Senator Feinstein has introduced a bill that will â€Å"lock up† a sexual offenders convicted twice of sexual crimes. He stated that the senator has received no opposition from her colleagues. It is unknown if she consulted with mental health practitioners, social workers, or other professionals in order to determine the efficacy of her bill or alternatives to incarceration, such as treatment to prevent recidivism. The policy implementing stage. Law enforcement agencies, parole agents, and other designated practitioners are being directed to enforce Megan’s Law. Each state is implementing Megan’s Law differently. For example, in California all sex offenders—whether adult or juvenile—must register. Communities will be notified of adults classified as â€Å"high risk† or â€Å"serious† sex offenders. (See Appendix D). There are 70,000 sex offenders in California. It is uncertain how many of these will eventually be classified as â€Å"high risk† or â€Å"serious† offenders. Policy assessing stage. The ACLU and Lambda Legal Defense and Education fund (LLDEF) have joined together to challenge this law on constitutional grounds. The ACLU and LLDEF argue that in many cases notification does more harm than good. They conclude that if information is to be disclosed publicly, it must be limited to that necessary to counteract the offender’s dangerousnous. ( ACLU, press release, August 19, 1994). Still, Megan’s Law is being implemented. In Placencia, California, police notified the community that a twice-convicted child molester, Sid Landau, was residing in their community. The community responded by organizing demonstrations in front of his residence. Some threatened him. Mr. Landau had to obtain legal representation in an attempt to stop the harassment. According to his lawyer, T. Matthew Phillips, Mr. Landau has been through â€Å"hell.† He argues that his client has been unfairly singled-out, that he paid for his crimes and should not be permitted to reenter society. Detective Corinne Loomis of the Placencia Police Department had hoped that people would eventually accept that Mr. Landau and others like him are going to be living in the community, and to appreciate that the best response is be aware and protective. That is what Megan’s Law was designed to do,† she said. â€Å"It was not designed to whip people into frenzy and have them run somebody out on a rail† (L.A. Times, 3-8-97). On April 25, 1997, Sid Landau was arrested for assaulting a cameraman who was following him. In another case, an 18-year-old male from Wisconsin was convicted of a â€Å"lewd act with a minor.† He faces 40 years in prison and, if convicted, he will have to register as a sex offender for life. This young man’s crime was having consensual sex with his 15-year-old girlfriend. The girlfriend got pregnant, and the young man dropped out of school in order to marry and support the girl. A social worker reported this case to the prosecutor’s office, and he was charged and convicted. The young man has the support of his community and plans to appeal his conviction. THE INTERVIEWS In this section I disucss two interviews I conducted regarding Megan’s Law. I could have interviewed anyone because we will all be involved with this law: law enforcement, which will be responsible for notifying citizens, as well as average citizens who happen to live in communities into which sex offenders are released. 1) Jacqueline Waltman Parole agent, California Department of Corrections. Ms. Waltman supervises adult parolees in the San Fernando Valley. 2) Gail Blucher Mother and President of the local Parents and Teachers Association (PTA). Ms. Blucher is resident of the Santa Clarita Valley. Ms. Waltman does not agree with Megan’s Law as it is written. Although she will be obliged to enforce it, she believes that many sex offenders will go â€Å"underground† in order to avoid registration requirements. Once underground, Ms. Waltman argues, these individuals will be more likely to molest more children. Further, she believes that a state of anxiety will be created in the communities encouraging the growth of vigilante groups. She believes her job will be more difficult as a result of supervising parolees in a community that is openly hostile to the parolees’ presence. She recognizes that the Department of Corrections does not provide sex offenders with effective therapy, if it provides any at all. Moreover, she stated that many sex offenders are warned by prison guards not to disclose their crime to fellow inmates so as not to provoke attacks upon themselves. Therefore, many do not request therapy during incarceration. Parole agent Waltman believes that sex offenders cannot be rehabilitated and should remain in prison for the rest of their lives. She nevertheless hopes that they can be treated and rehabilitated. She stated that her priority will always be the safety and protection of children. Jacqueline Waltman works part-time for the Los Angeles County Department of Children and Family Services at the Emergency Response Command Post (ERCP). She worked full-time for more than twenty years for the same department. Mrs. Blucher is a full-time homemaker and she is very involved in her seven-year-old daughter’s extracurricular activities. She is married. She has recently gotten involved with the â€Å"neighborhood watch† community program that works with the local sheriff’s department. Mrs. Blucher is anxiously anticipating Megan’s Law. She believes, quite obviously, that children need a safe neighborhood, and supports notification . However, she stated that she could not participate in â€Å"evicting† anyone from her neighborhood, but did not want sex offenders to live anywhere near her family. She strongly believes that sex offenders never change. She stated that the criminal justice system releases criminals too early, especially sex offenders. She supports Assemblyman Bob Margett’s (R-Arcadia) bill requiring that convicted child molesters wear electronic monitoring bracelets upon their release from prison. (I contacted the Assemblyman’s office regarding this bill. His aide reported that the bill passed without any opposition). She is looking forward to working with the â€Å"neighborhood watch† program to make children aware that her house is a designated safe house and that they are allowed to request assistance if they needed too. LETTER TO EXECUTIVE DIRECTOR RAMONA RIPSTON- ACLU 15920 Calle El Capitan Green Valley, CA 91350 Ms. Ramona Ripston Executive Director American Civil Liberties Union 1616 Beverly Blvd. Los Angeles, California, 90026 April 24, 1997 Dear Ms. Ripston My name is Xiomara Flores-Holguin and I am a graduate social work student at the University of Southern California. I am writing you in support of the American Civil Liberties Union, Southern California chapter’s position on Megan’s Law. I agree with the ACLU’s argument that notifying communities of sex offenders’ presence may cause more harm than good. First, released sex offenders are going to live somewhere. I am concerned about â€Å"not-in-my-backyard† vigilantism that will encouraged if citizens are not properly educated on bounds of appropriate action to take when notified of the presence of a sex offender in their communities. Second, there is little evidence that the Department of Corrections addresses the problem when the sex offenders are in prison. They cannot reassure society that these sex offenders are rehabilitated because they do not provide them any treatment. Also, we cannot forget that many former â€Å"sex offenders† have never presented a threat to society. I refer to gay people convicted of lewd acts for engaing in consensual sex with other adults. Will Megan’s Law require that these victims of homophobia be identified as â€Å"sex offenders† living in our midst? I wanted to express my appreciation and gratitude to the American Civil Liberties Union for your ongoing work in defending the Constitution of ALL people, whether we like them or not. Thurgood Marshall once asked, â€Å"Mental health and the law what if anything do they have in common?† He responded that both are concerned with the aspirations and problems of the human condition, and both deal with human rights and human responsibilities. Let us continue in our commitment to work on behalf of ALL people. Thank you. Sincerely, M. Xiomara Flores-Holguin MSW Graduate Student CONCLUSION At the beginning of this assignment, I believed that I had a strong position as to Megan’s Law and felt that this law was almost perfect. However, as a social worker, I recognized that the law was supported by little empirical research. I realize that no policy analysis is ever complete, that it is impossible to discover all of the data (data are essentially infinite) and to ask all of the possible questions. Policy analysis is always an approximation of the ideal and, as such, decisions are always made on the basis of incomplete data (Karger Stoesz, 1994). Karger and Stoesz (1994) argue that despite a nominal reliance on an analytical framework, social policy analysis in the â€Å"real world† is to some degree always biased. Because policy is analyzed by human beings, it is always done through the mirror of the analyst’s value system, ideological beliefs, and particular understanding of the goals and purposes of social welfare. Subjectivity is reflected in the omission (conscious or otherwise) of facts or questions, or in the relative weight given to one variable at the expense of others. Also, political pressure may be put on the policy analyst to come up with recommendations that are acceptable to a certain interest group. Regardless of the causes of subjectivity, policy analysis is always an approximation of the ideal, in effect an informed anticipation as to the effects of a policy or a set of policies. I believe that we need to stop crime against children in this generation. Furthermore, we need to identify and help those children that will be capable of continuing this cycle of crime as adults. The imprisoned sex offender, the released sex offender, and the unknown sex offender were children once, too. We should therapeutically treat the juvenile as soon as they are identified as potential offenders. We should not give up on people by â€Å"locking them up† An African proverb admonishes us, â€Å"It takes a village.† Let us take more responsibility. I will be pursuing a Community, Organization, Planning and Administration, concentration next year. I realized long ago that I wish to empower clients and advocate for them. I want to do so at the macro level. REFERENCES American Civil Liberties Union. (August 19, 1994). Press Release. Registration and community notification of convicted sex offender. ACLU Washington Office publication. Bierker, S.B. (1989). About sexual abuse. Springfield, Illinois: Charles C. Thomas Publisher. Brown, J.M. , Gilliard, D.F., Snell, T.L. , Stephan, J.J., Wilson, D.J. (1996). Correctional populations in the United States. U.S. Department of Justice, Bureau of Justice Statistics : Washington, D.C. publication. Finn, P. (1997, February). U.S. Department of Justice, Statistics on sex offender community notification. Rockville, Maryland: National Institute of Justice Publications. Jansson, B. (1994). Social policy: from theory to policy practice. Pacific Grove: Brooks/Cole. Karger, H.J., Stoesz, D. (1994). American social welfare policy: a pluralist approach. New York: Longman. Nelson, B. J. (1984). Making an Issue of Child Abuse. Chicago: The University Press. Palmer, E. A. (1996). GOP pushes four crime bills through the House. Congressional Quarterly. p. 1305. Richardson, L. Target of Megan’s Law Moves, Causing Stir. Loa Angeles Times, March 8, 1997, p.A20. Schopf, Simon (1995). â€Å"Megan’s Law†: Community notification and the Constitution. Columbia Journal of Law. 29 (117), 118-146. Welch, M.J. (1994). Press Release. Publicizing child molesters in your community. Personal mailing.

CuH-mediated Hydroamination of Styrene

CuH-mediated Hydroamination of Styrene Abstract: A detailed computational exploration of mechanistic intricacies of the copper(I) hydride (CuH)-catalysed hydroamination of styrene with a prototype hydoxylamine ester by a recently reported (dppbz)CuH catalyst (dppbz ≠¡ {P^P} ≠¡ 1,2-bis(diphenylphosphino)benzene) is presented. A variety of plausible mechanistic avenues have been pursued by means of a sophisticated computational methodology, from which a general understanding of the factors controlling hydroamination catalysis emerged. The catalytically competent {P^P}CuI hydride, which is predominantly present as its dimer, involves in irreversible hydrocupration proceeding with complete 2,1 regioselectivity to form a secondary {P^P}CuI benzyl intermediate. Its interception with benzylamine ester produces the branched tertiary amine product and {P^P}CuI benzoate upon intramolecular SN2 disruption of the amine electrophiles N-O linkage to precede highly rapid, strongly exergonic C-N bond-forming reductive eliminati on. The {P^P}CuI benzoate corresponds to the catalyst resting state and its conversion back into the {P^P}CuI hydride upon transmetalation with a hydrosilane is turnover limiting. The effect of electronic perturbations at the amine electrophile upon the reaction rate for productive hydroamination catalysis and also non-productive reduction of the hydroxylamine ester has been gauged, which unveiled a more fundamental insight into catalytic structure-performance relationships. Introduction The catalytic hydroamination (HA) reaction, the direct addition of an N-H bond across an unsaturated carbon-carbon linkage, offers facile access to an industrially relevant organonitrogen commodity and fine chemicals in a green, waste-free and highly atom-efficient manner.[1] By focusing on late d-block metal catalysis, several distinct mechanistic pathways have been revealed over the years for the hydroamination of alkenes, including the following principal processes: 1) N-H bond activation with subsequent alkene insertion into the metal-NR2 linkage,[2] nucleophilic attack of an amine at a metal-bound alkene,[3] nucleophilic attack of a metal amido species at an activated alkene[4] and amine coordination to be followed by proton transfer onto an activated alkene.[5] Despite the significant progress achieved over the past years the utilisation of these methodologies is still limited by a number of drawbacks.[1] The development of a general approach for regio- and enantioselective hyd roamination of a broad range of alkene substrate classes, in particular, remains an important challenge in the context of intermolecular HA. Recently, the groups of Miura[6] and Buchwald[7a] reported independently a mechanistically distinct approach for styrene HA that involves copper(I) hydride (CuH) as the catalyst together with amine electrophiles and a hydrosilane hydride source to furnish amines in excellent yields and enantio-/regioselectivities under mild conditions.[8] Miura and co-workers disclosed that styrenes react with benzylamine ester reagents in THF at room temperature to afford exclusively branched benzylic tertiary amines in the presence of a (dppbz)CuH catalyst (dppbz ≠¡ {P^P} ≠¡ 1,2-bis(diphenylphosphino)benzene) and a hydrosilane hydride source (Scheme 1).[6] Treatment of the Cu(OAc)2/dppbz starting material with Li(OtBu) and a reducing agent likely gives rise to {P^P}Cu(OtBu) 2, which becomes converted into the catalytically competent {P^P}CuI hydride 3 through transmetalation with silane. According to plausible mechanistic pathways outlined in Scheme 2 styrene insertion into the Cu-H linkage at 3 leads to {P^P}CuI alkyl 4 that couples with the benzylamine ester electrophile thereafter to generate amine product P and {P^P}CuI benzoate 6. Various mechanistic pathways can be envisaged for this transformation,[9] but its precise details remain largely elusive thus far. Transmetalation of 6 with hydrosilane regenerates the catalytically competent {P^P}CuI hydride for another catalyst turnover. The performance of HA catalysis via the productive cycle can be compromised by the well known aptitude of the {P^P}CuI hydride to reduce the amine electrophile. This may proceed through various pathways to involve formation of either N-H (one plausible path via a {P^P}CuIII benzoate amido hydride intermediate 7 is exemplified in Scheme 2) or O-H bonds to afford {P^P}CuI benzoate 6 by consumption of a molar equivalent of the amine electrophile. Precise knowledge of both the operative mechanism and of catalytic structure-performance relationships are indispensable for the rational design of improved HA catalysts. In light of the fact that precise details of mechanistic intricacies of CuH-mediated vinylarene HA remain largely elusive thus far,[10] a sophisticated computational protocol has been employed as an established and predictive means to study reaction mechanisms and to guide rational catalyst design. The present study scrutinises rival mechanistic pathways for HA of styrene (1a ≠¡ S) with O-benzoyl-N,N-dimethyl-hydroxylamine (1b ≠¡ A) by a catalytically competent dppbz-ligated CuI hydride complex in the presence of prototype trimethylsilane (1c ≠¡ H) as hydride source. No structural simplification (other than replacing O-benzoyl-N,N-diethyl-hydroxylamine and HSiPh3 used in experiment by 1b and 1c, respectively, solely for the purpose of computational efficiency) of any kind has been imposed for any of t he key species involved. The computational methodology employed (highly accurate DLPNO-CCSD(T) in conjunction with basis sets of def2-TZVP quality and a sound treatment of bulk solvent effects) simulated authentic reaction conditions adequately and mechanistic analysis is based on Gibbs free-energy profiles. This computational protocol can confidently be expected to reliably map the energy landscape and this has allowed mechanistic conclusions with substantial predictive value to be drawn. As detailed herein, our comprehensive mechanistic examination provides support that effective HA catalysis involves irreversible hydrocupration with strict 2,1 regioselectivity to be followed by generation of the branched tertiary amine product by interception of the thus formed secondary {P^P}CuI benzyl nucleophile with amine electrophile. The prevailing pathway sees the first intramolecular SN2 displacement of the benzoate leaving group and is followed by highly facile and strongly exergonic C-N bond-generating reductive elimination from a highly reactive, intervening {P^P}CuIII species. It leads to amine product and {P^P}CuI benzoate, the latter of which corresponds to the catalyst resting state. Its conversion back into the catalytically competent {P^P}CuI hydride is turnover limiting. Results and Discussion The aim of the present study is twofold. A first part scrutinises thoroughly all the relevant elementary steps of Scheme 2, with special attention devoted to the several mechanistic avenues that can be invoked regarding the interaction of {P^P}CuI alkyl nucleophile with the amine electrophile and also the productivity-limiting reduction of the amine transfer agent. A second part explores the effect of electronic perturbations at the amine electrophile upon catalyst performance. {P^P}CuH-mediated HA of styrene with amine electrophile 1b Catalyst initiation Effective HA catalysis entails the initial conversion of {P^P}Cu(OtBu) 2 into the catalytically competent {P^P}CuI hydride compound. The ability of hydrosilane 1c (≠¡ H) to affect transmetalation at 2, although being rather unlikely turnover limiting, will influence the performance of HA catalysis, since it determines the amount of catalytically competent {P^P}CuI hydride species available for catalyst turnover. Hydroxylamine ester 1b (displaying a slight preference for à ¯Ã‚ Ã‚ «1-N over à ¯Ã‚ Ã‚ «1-O donor ligation) and THF (T) show a comparable aptitude to bind at copper in 2. However, the entropic costs linked with reactant association place the respective adducts 2†¢A, 2†¢T higher in free energy relative to the separated fragments. This gap widens regularly for ever weaker donor molecules as clearly seen in Figure 1 for silane (2†¢H) adducted species. Furthermore, 2 exhibits no propensity toward dimer formation, as all the efforts to localise a dimeric species failed. After the initial facile, but uphill association of trimethylsilane 1c at 2, transmetalation evolves through a metathesis-type transition-state (TS) structure (see Figure S1 in the Supporting Information), which decays thereafter into the {P^P}CuI hydride complex 3 through facile liberation of Me3SiOtBu. Figure 2 reveals an affordable kinetic barrier (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 22.4 kcal mol-1 relative to {2 + 1c}) for conversion of 2 into the catalytically competent complex 3, which is driven by a thermodynamic force of substantial amount. {P^P}CuI hydride compound Reactant (styrene S, hydroxylamine ester A, hydrosilane H), amine product (P) and THF (T) solvent molecules can associate in various ways at copper in the catalytically competent hydride compound (see Figure S2 in the Supporting Information) to give rise to a multitude of adducted species, all of which are expected to participate in mobile association/dissociation equilibria.[11] Similar to what is found for 2, the copper centre can accommodate only a single molecule;[13] its moderate binding enthalpy, however, cannot compensate for the associated entropic costs, thereby rending the various adducted species to be higher in free energy than the respective separated fragments. Amines (A, P) and styrene (benefitting from coppers ability for backbonding) are found to associate preferably and hence 3†¢A, 3†¢S display an energy gap (relative to separated fragments) that is somewhat smaller than for 3†¢T and 3†¢H (Figure 3). On the other hand, 3 exhibits a pronounced pro pensity towards dimer formation with 3dim is favoured by 7.5 kcal mol-1 relative to 3 (Figure 3). Hence, the catalytically competent {P^P}CuI hydride is predominantly present as dimer 3dim with relevant adducts 3†¢S (productive cycle, Scheme 2) and 3†¢A (non-productive cycle, Scheme 2) are well separated and higher in free energy by more than 12 kcal mol-1 (Figure 3). Styrene insertion into the Cu-H linkage Following the plausible catalytic scenario in Scheme 2, the productive cycle entails the first generation of {P^P}CuI alkyl 4. Alternative regioisomeric pathways for migratory C=C bond insertion into the Cu-H à ¯Ã‚ Ã‚ ³-bond commencing from 3†¢S have been examined. The possible participation of another reactant, amine product or solvent molecule has been probed explicitly, but neither encounter, product or TS structures featuring a stable coordination of a spectator molecule could be located.[13] Common to both pathways for 1,2 and 2,1 insertion is the evolution of C-H bond formation through a four-centre planar TS structure describing metal-mediated migratory insertion of the styrene C=C linkage into the polar Cu-H bond, which occurs at distances of 1.57-1.65 Ã… (see Figure S3 in the Supporting Information) for the emerging C-H bond. Following the reaction path further, TS structures decay into primary {P^P}CuI alkyl 4b (1,2 insertion) and secondary {P^P}CuI benzyl 4a (2,1 insertion), respectively. Effective delocalisation of electron density is known to markedly influence the stability of the polarised TS structure describing the interaction of an electron-rich Cu-H à ¯Ã‚ Ã‚ ³-bond with the styrene C=C linkage and also of 4, such that the regioselectivity of the hydrocupration is largely dictated on electronic grounds.[14] The  °-electron-withdrawing arene functionality at the styrene carbon directly adjacent to the copper centre effects an effective depletion of electron density from the nonsubstituted olefinic CH2 centre in the TS structure and also assist through hyperconjugative interaction with the stability of 4a. Hence it electronically stabilises both the TS structure for 2,1 insertion and 4a when compared to the species involved in 1,2 insertion that are devoid of such an opportunity. The located TS and product species (see Figure S3 in the Supporting Information) give no indication that the electronic predisposition towards 2,1 insertion is likely to be reversed due to favourable {P^P}Cu-arene interactions along the 1,2 pathway. Thus, 2,1 insertion is expected to prevail energetically on both kinetic and thermodynamic grounds. Indeed, Figure 4 reveals that migratory olefin insertion proceeds with complete 2,1 regioselectivity to afford secondary {P^P}CuI benzyl 4a by overcoming a barrier of 21.6 kcal mol-1 (à ¯Ã‚ Ã¢â‚¬Å¾G relative to 3dim), whereas the 1,2 pathway remains inaccessible due to higher kinetic demands (à ¯Ã‚ Ã¢â‚¬Å¾Ãƒ ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 4.1 kcal mol-1) and is also disfavoured thermodynamically (à ¯Ã‚ Ã¢â‚¬Å¾Ãƒ ¯Ã‚ Ã¢â‚¬Å¾G = 4.4 kcal mol-1). It characterises hydrocupration via the energetically prevalent 2,1 pathway to be kinetically viable and irreversible.[15] Amine product generation upon interception of 4 by amine electrophile The interception of {P^P}CuI alkyl 4 with amine electrophile 1b gives rise to the generation of amine product P and releases {P^P}CuI benzoate 6 (Scheme 2). Various mechanistic scenarios are conceivable for this transformation,[9] but, unfortunately, virtually no precise details of the operative mechanism are available.[10] This section intends to fill this gap by thoroughly examining several rival pathways. It includes the cleavage of the hydroxylamine ester N-O linkage via: 1) SN2 displacement of the benzoate leaving group; 2) intramolecular SN2 displacement; and 3) oxidative addition across the N-O linkage. This affords transient {P^P}CuIII intermediate 5, from which P and 6 are likely formed upon C-N bond-forming reductive elimination. The generation of the branched tertiary amine product Pa in a single step through nucleophilic attack of the Cu-C linkage at the positive N(amine) centre with concomitant N-O bond cleavage has been probed as a further plausible mechanistic avenue ( dashed arrow in Scheme 2). Given that hydrocupration proceeds with strict 2,1 regioselectivity, the discussion will focus exclusively on pathways that commence from 4a. Notably, rival paths starting from 4b are found energetically non-competitive in every case studied. The full account of all the studied pathways can be found in the Supporting Information. We start with examining N-O bond cleavage of 1b by nucleophilic {P^P}CuI benzyl 4a. Figure 5 collates the free-energy profile of the most accessible pathway for the various mechanistic scenarios examined, whilst structural aspects of key species involved can be found in Figures S4-S9 (see the Supporting Information). The electrophile 1b binds preferably via its N donor centre (à ¯Ã‚ Ã‚ «1-N) at copper to furnish adducts with the unbound carboxylate oxygen pointing either towards (4a1†¢A) or away (4a2†¢A) from the metal, both of which are higher in free energy than the separated fragments. The located TS[4a2†¢A5a] structure describes N-O bond cleavage that is reminiscent of a SN2 displacement of the benzoate group, featuring distances of 1.72 and 2.02 Ã… for vanishing N-O and emerging Cu-N amido bonds (see Figure S5 in the Supporting Information). Progressing further along the reaction trajectory, the benzoate group binds eventually at copper to deliver transient { P^P}CuIII intermediate 5a. The intramolecular process version commencing from 4a1†¢A evolves through a five-centre TS[4a1†¢A-5a] that displays similar metrics regarding vanishing N-O and emerging Cu-N amido bonds, but crucially benefits from an already pre-established Cu-O(benzoate) contact (see Figure S7 in the Supporting Information). As it turns out, this contact likely renders 4a1†¢A→5a intramolecular SN2 displacement somewhat favourable kinetically over 4a2†¢A→5a with both pathways are indistinguishable on thermodynamic grounds. The TSOA[4a2†¢A-5a] shown in Figure 5 (see also Figure S9 in the Supporting Information) has been located as energetically prevalent three-centre TS structure describing oxidative addition across the N-O linkage that occurs at distances of 2.43 Ã… and 1.89/2.60 Ã… for vanishing N-O and newly built Cu-N(amido)/Cu-O bonds, respectively. The condensed free-energy profiles in Figure 5 reveal that for cleavage of the electrophiles N-O linkage by {P^P}CuI benzyl nucleophile the 4a1†¢A→5a intramolecular SN2 pathway (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 19.8 kcal mol-1 relative to {4a+1b}) prevails kinetically somewhat over 4a2†¢A→5a, with oxidative addition proceeding through TSOA[4a2†¢A-5a] (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 31.1 kcal mol-1 relative to {4a+1b}) is found substantially more demanding kinetically and hence not accessible. The fine energy balance between the alternative SN2-type pathways is likely be influenced by the diphosphine catalyst backbone. Figure 6 combines the dominant pathway for N-O bond cleavage at amine adduct 4a†¢A with C-N bond-generating reductive elimination at transient {P^P}CuIII 5a taking place thereafter. Given that benzyl and amido functionalities are already preferably arranged in 5a no major structural reorganisation is required prior to traversing TS[5a6†¢Pa], which occurs at a distance of 2.36 Ã… of the emerging C-N bond (see Figure S11 in the Supporting Information) and decays thereafter into the branched tertiary amine product that is initially bound to {P^P}CuI benzoate (6†¢Pa), but is readily released thereafter. The reductive elimination is found highly facile (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 5.2 kcal mol-1 relative to 5a) and driven by a remarkably strong thermodynamic force (Figure 6). Of the two consecutive steps converting {P^P}CuI benzyl 4a into amine product Pa and {P^P}CuI benzoate 6 through interception with electrophile 1b, the first intramolecular SN2 displacement of the ben zoate leaving group determines the overall kinetic demands (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 19.8 kcal mol-1 relative to {4a+1b}) with Pa and 6 are then generated from transient, highly reactive {P^P}CuIII intermediate 5 upon rapid and strongly downhill reductive elimination. Nucleophilic attack of the Cu-C linkage at the positive N centre of the amine electrophile with concomitant N-O cleavage, thereby affording 6a + Pa in a single step, describes an alternative mechanistic scenario. Despite all our efforts, a precise TS structure associated to this pathway could not be located, but examination by means of a state-of-the-art reaction-path-optimisation (chain-of-state; see the Computational Methodology) method provided a reasonably approximate TS structure. The multicentre TS[4a1†¢A-6†¢Pa] describes concerted N-O bond cleavage (2.30 Ã…) together with C-N (2.54 Ã…)/Cu-O(2.37 Ã…) bond formation, all occurring in the immediate vicinity of the copper centre (see Figure S12 in the Supporting Information). A substantial barrier of approximately 30.7 kcal mol-1 (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ relative to {4a+1b}) has to be overcome (Figure 7), which renders the concerted 4a1†¢A→6†¢Pa pathway non-accessible kinetically in the presence of the viable two-step conversion shown in Figure 6.[16] {P^P}CuI benzoate compound In light of the strong thermodynamic force associated with generating the C-N bond, the {P^P}CuI benzoate may become, among others, a candidate for the catalyst resting state. Hence, the aptitude of 6 to accommodate additional reactant, amine product and THF solvent molecules has been probed in order to clarify its precise identity. In accordance with findings for 2 and 3, a single molecule only can bind at copper at the expense of one of the two Cu-O(carboxylate) linkages, but adduct formation is disfavoured in terms of free energy. Hence the {P^P}CuI benzoate is predominantly present as non-adducted form 6 featuring a à ¯Ã‚ Ã‚ «2-O ligated benzoate functionality (Figure 8). Regeneration of {P^P}CuI hydride from {P^P}CuI benzoate Transmetalation of 6 with trimethylsilane 1c regenerates the catalytically competent {P^P}CuI hydride 3 for another catalyst turnover, thereby closing the cycle for productive HA catalysis. Two scenarios have been analysed that are distinguished by which of the carboxylate oxygens at silane adducted 6†¢H participate in Si-O bond formation. The transfer of silyl onto the oxygen directly bound to Cu evolves through a four-centre metathesis-type TS[6†¢H-3†¢OS1] and leads eventually to 3 upon facile liberation of Me3SiOBz. On the other hand, a six-centre TS[6†¢H-3†¢OS2] is traversed along an alternative pathway representing silyl transfer onto the unbound carboxylate oxygen (Figure 9 and Figure S13 in the Supporting Information). The enhanced stability of six-centre TS[6†¢H-3†¢OS2] versus four-centre TS[6†¢H-3†¢OS1] discriminates among the two pathways, which are driven by a thermodynamic force (à ¯Ã‚ Ã¢â‚¬Å¾G = 0.5 kcal mol-1 relative to {6 + 1c}) of identical magnitude. The assessed barrier of 26.2 kcal mol-1 (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ relative to {6 + 1c}) for the most accessible pathway characterises 6 + 1c→3 + Me3SiOBz as a kinetically demanding, but viable transformation that is slightly uphill thermodynamically (Figure 9). Reduction of the benzylamine ester by {P^P}CuI hydride The well known tendency of the catalytically competent {P^P}CuI hydride to reduce the amine electrophile under N-H bond formation, hence giving rise to {P^P}CuI benzoate, or alternatively via O-H bond formation to afford a {P^P}CuI amido can severely compromise the catalyst performance. To this end, several conceivable pathways (some of which are sketched in Scheme 2) have been studied. Whilst focusing on thermodynamic aspects amine reduction with N-H bond formation via 3 + 1b→6 + HNMe2 (à ¯Ã‚ Ã¢â‚¬Å¾G = -71.9 kcal mol-1) appears to be strongly favoured over O-H bond generating 3 + 1b→{P^P}CuI(NMe2) + benzoic acid (à ¯Ã‚ Ã¢â‚¬Å¾G = -51.3 kcal mol-1). The cleavage of the N-O linkage of 1b at amine adduct 3†¢A does preferably proceed through SN2 displacement of the benzoate leaving group with the intramolecular pathway proved to be somewhat favourable energetically (see Figure S14 in the Supporting Information), whilst oxidative addition of electrophile 1b across the N-O linkage is found substantially more demanding kinetically. All these aspects closely parallel the findings regarding the preferable avenue that leads to generate {P^P}CuIII 5a (see above). Likewise, N-H bond-forming reductive elimination at {P^P}CuIII amido hydride intermediate 7 is highly facile kinetically and strongly downhill as 5a→6a + Pa is. Unfortunately, all the efforts to localise the associated TS structure have not been successful, but the examination of the reaction path thoroughly by means of a chain-of-state method firmly indicates that reductive amine elimination at 7 has an only marginal barrier, if at all, to overcome, hence it proceeds almost instantaneously. Overall, a smooth, kinetically affordable pathway for undesired 3 + 1b→6 + HNMe2 conversion has been located that comprises a first intramolecular SN2 cleavage of the N-O bond (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 26.3 kcal mol-1 relative to 3dim, Figure 10), to be followed by highly rapid reductiv e amine elimination from an intervening and highly reactive {P^P}CuIII intermediate 7, thus reflecting the well-documented aptitude of 3 to engage in performance-limiting reduction of the electrophilic amination reagent.[6, 7] Further attempts devoted upon locating a proper TS structure for the concerted attack of the nucleophilic Cu-H linkage at the N centre of the amine electrophile to be accompanied with N-O bond disruption has not been successful. However, a reasonably approximate TS (see Figure S15 in the Supporting Information) is seen to be above TS[31†¢A-7] by another 19.8 kcal mol-1, such that the concerted pathway can confidently be discarded as energetically viable alternative to the operative two-step process. Proposed catalytic cycle The mechanistic picture based upon the above thoroughly conducted examination of relevant elementary steps is presented in Scheme 3. An energetically smooth and downhill sequence of steps transforms the starting material into the catalytically competent {P^P}CuI hydride 3, which is in a mobile equilibrium[11b] with its thermodynamically prevalent dimer 3dim. Migratory insertion of the styrene C=C linkage into the Cu-H bond is kinetically facile (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 21.6 kcal mol-1 relative to { ½3dim+1a}), thermodynamically downhill and proceeds with strict 2,1 regioselectivity. Hence irreversible hydrocupration is regioselectivity determining and occurs prior to the turnover-limiting step. The interception of the thus generated secondary {P^P}CuI benzyl 4a with amine electrophile 1b produces the branched tertiary (Markovnikov) amine product Pa and {P^P}CuI benzoate 6. This transformation favours a two-step process comprising the first intramolecular SN2 displacement of the b enzoate leaving group (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 19.8 kcal mol-1 relative to { ½3dim+1a+1b}) to furnish transient, highly reactive {P^P}CuIII intermediate 5 from which Pa and 6 are generated upon highly rapid and strongly downhill reductive elimination. It renders 6 to be the most stable species of the cycle for productive HA catalysis and it thus corresponds to the catalyst resting state. The regeneration of catalytically competent 3 from 6 through transmetalation with hydrosilane 1c is found most demanding, but affordable, kinetically (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 26.2 kcal mol-1 relative to {6+1c}) and hence is turnover limiting its assessed barrier is compatible with reported catalyst performance data.[6] It is worth mentioning that a similar picture regarding hydrocupration and transmetalation steps has emerged from a recent experimental study by the Buchwald group on a DTBM-SEGPHOS-based CuI catalyst.[7d] A stepwise pathway closely related to 4a†¢A→6 + Pa is preferably traversed for the non-productive reduction of amine electrophile by 3. An intramolecular SN2 N-O bond disruption (à ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 26.3 kcal mol-1 relative to { ½3dim+1b}) precedes highly facile and strongly downhill reductive amine elimination from intervening, highly reactive {P^P}CuIII intermediate 5a. The assessed small kinetic gap (à ¯Ã‚ Ã¢â‚¬Å¾Ãƒ ¯Ã‚ Ã¢â‚¬Å¾G†¡ = 0.1 kcal mol-1) between discriminative TS structures for productive and non-productive reaction branches reflects adequately the observed close competition between the two processes, which can lead to compromised catalyst performance for improper chosen amine electrophiles. Furthermore, it provides further confidence into the substantial predictive ability of the herein employed high-level computational methodology.[17] Effect of the amine electrophile upon catalyst performance A second part of this study explores the effect of the amine electrophile upon catalyst performance. To this end, the energy profile for two