Film as art Essay Example | Topics and Well Written Essays - 1000 words

Film as art - Essay Example The twist in the story comes when Sean realizes that he could not be the reincarnation of Anna’s husband since he had loved another woman while he was in his previous life. Anna and Sean stop seeing each other, though they continued to write letters on occasion. Anna married Joseph, finally obtaining the closure that she desperately needed. The film opens with a black screen and a voice over of adult Sean explaining his disbelief in the concept of reincarnation. Despite this, he makes it known that if Anna died and were to come back as a bird, he would be accepting of it and continue to live with her. The scene that follows is a continuous long shot of Sean running through bleak and wintry Central Park. Sean’s face is never revealed to us, making him an abstract character regardless of his importance to the story. This lack of identity begins the mystery of who Sean really is. Nothing else is revealed about Sean except that he dies from a heart attack while jogging. Imm ediately after Sean’s death, the shot cuts abruptly to a clip of a baby being born, emerging from the water of a birthing tub. The following scene, after script reads Ten years later, Anna is shown standing at the grave of her late husband. The quick scene jumps reveal how all three events - Sean’s death, the baby’s birth, and Anna paying respect to her husband - are closely related to one another (Ebert, 2004). The shots, though clearly different from one another, are shown so quickly that they could have easily been one in the same, revealing the same message -- the never-ending cycle of life and death. Grazer uses only a few different camera angles and shots in the film, but his decision on what angles and shots to use and when helps to show the torment that Anna is experiencing as she continues to suffer from her husband’s death and as she tries to come to terms with the presence of young Sean. For example, the sex scene between Anna and Joseph begins as a medium close-up, but the slowly camera pulls back into a long shot as Anna discusses young Sean’s pleas for Anna not to marry Joseph. This sudden distance shows how far apart from Joseph that Anna is, even though they could not be any closer to one another. The physical distance between the camera and the couple reveals the mental and emotional distance that Anna is from Joseph. Another intense camera shot is the continuous close-up of Anna while she is at the orchestra. The music, similar to what is heard throughout the rest of the movie, picks up with intensity the longer that the camera rests on Anna, displaying the emotional changes that she goes through in the elongated scene. Anna’s features â€Å"run the full gamut of traumatized emotions, from barely suppressed terror, through claustrophobic anxiety, to heartbreaking acceptance (Kermode 45).† This is when Anna fully comes to accept that young Sean is who he claims to be. Grazer also plays on the me aning of color in the movie, implementing green in many scenes. The walls of Anna’s apartment kitchen are green, as are Sean’s sweatshirt, the blanket he uses while staying overnight at Anna’s, and the couch. The color green represents balance, life, and wellbeing (Ascher & Pincus 122), which are three important aspects seen constantly in the film. Green appears with Anna and Sean, separately, but also when they

European Court of Justice Essay Example for Free

European Court of Justice Essay The European Union (EU) is a celebrated alliance of Nations that runs from the United Kingdom and Portugal in the West to Turkey in the East. The EU has made travel and trade much easier between its member states. With few exceptions this Union now shares a common currency known as the Euro. After close to a decade of existence the Euro is now stronger than the U. S. Dollar. This economic powerhouse is energized by free trade between its members a free trade marked by cooperation rather than competition. Today, the average French Citizen has access to Limburger, Swiss and Italian Cheeses at ever cheaper prices. The EU can legitimately boast that it has all but eliminated tariffs between native states. Unfortunately, this Union is not without its faults. There are occasions when selfish national interest subvert the good of the Union. After all, despite the good will and benefits that nations gain from free trade, parochial interests can still sometimes over come the common good. In such cases the European Court of Justice may be forced to intervene. For example, In Commission v.  Italy Italian customs charges were struck down because any pecuniary charge, however small, imposed on goods by reason of the fact that they cross a frontier constitutes an obstacle to the movement of such goods. † Commission vs. Italy is not an isolated case, it is safe to say that â€Å"In developing the rules of the internal market, the European Court of Justice has maintained a careful balance between the de-regulation imperative of the Treaty, as interpreted by the Court, on the one hand, and legitimate Member State interests and the reality of regulatory diversity, on the other. The Court’s perception of the place of both civil and political rights and social rights within the internal market changes in accordance with how this balance falls. † The European Court of Justice (ECJ), also known as the Court of Justice of the European Communities is the highest court of the European Union. The court is similar to a national Supreme Court. It strives, interpret the EU laws to ensure equal application across the various European Union member states The European Court of Justice is based in Luxembourg City and was established in 1952. It is one of the few European Union institutions that is not based in Brussels. There is one judge for every member state although only thirteen can be present to hear a case at any given time. The ECJ has jurisdiction over all matter of European Community law, but can not intervene with respect to national law. Every nation has its respective national legal system which the Union must respect. However, the ECJ ensures that EU level legislation is interpreted and applied in equal manner across the whole of the EU. This prevents national Supreme Courts from interpreting the same legislation differently. The Courts decisions are binding. For instance, a state that fails to implement a directive or a Commission that acts outside its delegated power has to answer to the ECJ. The Court also has jurisdiction over cases involving disputes between states, institutions, businesses and individuals A full tale of the ECJs jurisdiction includes the insurance that the law is observed in the interpretation and application of the Treaties of the European Union. This application must be uniform across all nations without bias or favoritism, hence the need for a Union-wide arbiter of the law. The court must also see that the provisions are laid down by Community institutions with the proper competence. The Court enjoys a wide latitude to hear various actions. Among other things the court may rule on applications for annulment or actions for failure to act raised by a member state or institution, actions against Member States for failure to fulfill obligations, references for a preliminary ruling and appeals against decision of the Court of First Instance Under Article 226 of the Consolidated Treaty Establishing the European Community (CTEEC), the ECJ may determine if a Member State has fulfilled its obligations under Community Law. A preliminary hearing will allow the erring Member State to reply to the complaint. If the hearing does not result in termination of the claim of failure by the Member State an action for breach of Community law may be brought before the European Court of Justice. Such an action is ordinarily brought to the court by a Member State by another Member State. If the court finds that the claimed obligation has not been fulfilled the erring Member State must terminate the breach with due haste. If the breach is not resolved within a reasonable time period upon the Request of the Commission, the European Court of Justice may impose a fixed or periodic financial penalty. In addition the court may also act on Actions for Annulment, Actions for failure to act, Applications for compensation based on non-contractual liability. The court can also rule of review on point of the law. The ECJ is the final arbiter with respect to the interpretation and application of community law. The Court of First Instance, deals with most cases before they are elevated to the ECJ. However, these two bodies are not the only judicial body tasked with interpreting the application of Community Law. The true court of first instance is actually the national courts. The national courts retain jurisdiction to review the administrative implementation of Community law. , for which the authorities of the Member State are responsible. It is because of this role that the National courts are the first guarantors of the Community law. Unfortunately, National courts are beholden to the nations in which they belong. It cannot be helped but for a justice to give his loyalty first to his country and second to the Union. Cynicism aside, there can and there have been occasions were the parochial interest of the state was upheld by the National courts over the fair and equitable application of the EU’s laws. It is in these circumstance that the Court must intervene. In Costa vs ENEL it was established that Community law takes precedence over the member states domestic law. Furthermore, in Simmenthal II the Court held that there is a Duty to set aside provisions of national law which are incompatible with Community Law. Hence, the Court justifies its rulings in favor of Community law over the parochial decisions of National Courts. Despite criticism that at time the court has overstepped its bounds and has interfered with local laws. The powerhouse economy of the EU is made possible by the elimination of Tariff barriers that once plagued the nations. Tariffs historically, made products of one nation less competitive in the market of another nation. For example, all things being equal, a bottle of wine produced in France will cost more than Italian wine in Rome because the French wine had to pay Tariffs. Articles 23 and 25 of the EC prohibit all â€Å"customs duties on imports and exports and of all charges having equivalent effect. This applies between Member States and also applies to customs duties of a fiscal nature. The ECJ has remained steadfast in upholding the Union’s commitment to Free Trade. The ECJ has ruled that ‘Goods’ are â€Å"products which can be valued in money and which are capable, as such of forming the subject of commercial transactions . † Hence, painting, sculptures and even musical recordings are ‘goods’ the establishment of tariff barriers against is disallowed. Even waste is capable of forming the subject of a commercial transaction A criticism against the ECJ is that at times it may overstep its bounds and interfere with the internal workings of a nation. For example, in Diamantarbeiders ; â€Å"A charge having equivalent effect to a customs duty is any pecuniary charge however small and whatever its designation and mode of application which is imposed unilaterally on domestic or foreign goods by reason of the fact that they cross a frontier and which is not a customs duty in the strict sense. This is the case even if it is not imposed for the benefit of the State [and] is not discriminatory or protective in effect, or if the product on which the charge is imposed is not in competition with any domestic product. Also in Bresciani Charges imposed for a public health inspection carried out on the entry of goods to a Member State can be a charge having equivalent effect to a customs duty. It was not important that the charges were proportionate to the costs of the inspection, nor that such inspections were in the public interest . Thus, the ECJ continues to maintain its commitment to free trade and the removal of all barrier to trade between Member States. The efforts of non-compliant Member States to form covert or hidden tariffs is vigilantly watch by the Court in order for it to act swiftly and decisively upon any breech that arises However, Court is not wholly without heart or willingness to render judgment based on its jurisdiction as a court of Justice AND equity. It is not utterly insensitive to the plight of Member States. In commission vs Germany it ruled that; A charge for a service will not be regarded as a customs duty where it: (a) does not exceed the cost of the service, (b) that service is obligatory and applied uniformly for all the goods concerned, (c) the service fulfills obligations prescribed by Community law, and (d) the service promotes the free movement of goods in particular by neutralising obstacles which may arise from unilateral measures of inspection . This decision is of interest because of its Solomonic approach, Germany at that time was suffering a period of economic dislocation and in a nut shell needed to be cut some slack. By allowing charges for a service to be accounted as not a customs duty, it allowed Germany a quantity of income. Strict rules were established to ensure that such allowance is not abused by Germany or any other Member State. However, the European Court of Justice still upheld its commitment to free trade. Art 90 of the EC provides that Member States are prevented from imposing, â€Å"directly or indirectly, on the products of other Member States any internal taxation of any kind in excess of that imposed directly or indirectly on similar domestic products. In Humblot it was held that the prohibition extends to internal taxation of such a nature as to afford indirect protection of product†. This case was an example of how pervasive and at times invasive the European Court of Justice can get in upholding its mandate. The European Court of Justice has a mandate to protect the Community Law. At times it must do so over the heads of Member States who have put parochial interests before the good of the Union. Fortunately, the Court has been granted sufficient mandate and jurisdiction to uphold the its commitment to Free Trade. The Court is at times criticized for being too invasive and interfering even with the internal workings of a Member State. The Court is also lambasted from being overly committed and ignoring the facts of the ground, or the special circumstances which might merit certain exceptions. As was noted in the Germany case, this is not so. Despite its mandate, the Court remains sensitive to the needs of individual nations some of which may require some temporary consideration in order to adjust and eventually be full partners of the European Union.

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

Asian American Literature :: essays papers

Asian American Literature Asian Americans seem to be fighting an unwinnable battle when it comes to the content of their writing. Writers are criticized by whites for speaking out against discrimination, and by their fellow Asian Americans for contributing to the stereotypes through their silence. I believe that Asian Americans should include politics in their writing as they so choose, but should not feel obligated to do so, as Frank Chin suggests. For those Asian Americans who make known their discontent with the injustice and discrimination that they feel, in the white culture, this translates to attacking American superiority and initiating insecurities. For Mura, a writer who dared to question why an Asian American was not allowed to audition for an Asian American role, his punishment was â€Å"the ostracism and demonization that ensued. In essence, he was shunned† (Hongo 4) by the white people who could not believe that he would attack their superior American ways. According to writers such as Frank Chin and the rest of the â€Å"Aiiieeeee!† group, the Americans have dictated Asian culture and created a perception as â€Å"nice and quiet† (Chin 1972, 18), â€Å"mama’s boys and crybabies† without â€Å"a man in all [the] males.† (Chin 1972, 24). This has become the belief of the proceeding generations of Asian Americans and therefore manifested these stereotypes. Those authors who contest these â€Å"American made† stereotypes are said to betray the American culture and white power around them, and to be â€Å"rocking the boat† in a seemingly decent living situation. It is as though Asian Americans are succombing to the thought that America is the only place to be and that they should be grateful to live here. On the other hand, keeping silent due to pressures from the white population means being shunned by the members of the Asian American population. I disagree with Chin’s ascertation that â€Å"years of apparent silence have made us accomplices† to the makers of stereotypes (Chin 1991, xxxix). I agree with Hongo’s argument that Chin viewpoint â€Å"limits artistic freedom† (Hongo 4). Declaring that those writers who do not argue stereotypes of the good, loyal, and feminine Chinese man or the submissive female, are in any way contributing to or disagreeing with them is ridiculous. Chin’s opinion that politics should be included in some aspect of every Asian American piece eliminates choice from writing topics for other writers. Authors are the voices of the people (whichever people they choose to represent) and should not be criticized for choosing to discuss issues other than those that Chin deems necessary.

OXO: Satisfaction Guranteed Essay

OXO’s most profitable customers are those with dexterity problems like arthritis such as the wife its founder, Sam Farber, had when coming up with the idea of starting OXO. Now OXO designs products that are usable by as many people as possible. This means that men and women, young and old, left and right handed, and those with special needs can utilize their products (OXO, 1990). â€Å"Through market segmentation, companies divide large, heterogeneous markets into smaller segments that can be reached more efficiently and effectively with products and services that match their unique needs (Kotler & Armstrong, 2014).† Psychographic segmentation is primarily used by OXO in efforts to target a multitude of consumer’s with different lifestyles. Each OXO product â€Å"was developed based on the concept of Universal Design (also known as Inclusive Design), a philosophy of making products that are usable by as many people as possible (OXO, 1990).† Many of the com petitions kitchen gadgets from the research attempt to conform to the needs of consumers such as OXO has done. There are few that have reached the standard for universal ease of use. The value proposition that is extended to OXO’s clients is a satisfaction guarantee which is clearly stated on its website. â€Å"We guarantee everything we make! If for any reason you are not satisfied with an OXO product, return it for replacement or refund (OXO, 1990).† OXO’s satisfaction guarantee is similar to that of some of it’s competitors but not all. Companies such as CUTCO and CHEFS share the 100% satisfaction guarantee value proposition. In order for OXO to develop their product line to stand out from competitors â€Å"Smart Design’s first assignment was to come up with tools that were comfortable in the hand, dishwasher safe, high quality, good looking and  affordable.† OXO’s â€Å"designers divided tool types by wrist and hand motions: twist/turn (used to scoop, stir and peel), push/pull (graters and knives) and squeeze (scissors, garlic press and can openers).† 3 Levels of Product Core customer Value: What is the customer really buying? OXO’s customers are purchasing â€Å"wonderfully comfort–able tools that are easy to use (Corporate Design Foundation).† Actual product: brand name, quality level, packaging, design, features OXO’s hand tools are sold under the name Good Grips, chosen because â€Å"it communicates the major advantage of the line quickly,† explains Farber. OXO’s goal is to provide â€Å"budget–conscious consumers with tools that adhered to OXO’s principles of universal design, focusing on user comfort.† OXO makes grave attempts to use less plastic in packaging (Corporate Design Foundation). Augmented product: delivery and credit, product support, warranty, after-sale  OXO provides product support via email, phone, fax, and mail. The company’s satisfaction guarantee is a warranty within itself. Customers can return products for a replacement or a full refund. After researching OXO’s products it became very apparent that the company follows an intensive distribution strategy. Their products are found in many different shopping outlets such as JC Penny, Bed Bath and Beyond, Kohl’s, Amazon.com, and Sur La Table just to name a few. This type of distribution is very convenient for the company if they’re aim is to provide comfortable gadgets for all to use. Distributing to these types of stores appears to target all lifestyle groups. The pricing of OXO’s Good Grip products seem very reasonable in nature from the product prices I have seen recently. I’ve even purchased a few of the gadgets myself because the pricing and handiness. In comparison to like items, OXO adopted the correct pricing scheme and has made itself a viable competitor in the home goods market. OXO is doing what any other reasonable and profitable company is doing by advertising on social media sites. There is vast community of social media  users that can be pose as potential customers of OXO. Facebook and Twitter are the two most reputable social media sites and they OXO utilizes both to broaden its customer base. Facebook alone has: Over 1.15 billion users, one million webpages can be accessed with the â€Å"Login with Facebook† feature 23% of Facebook users login at least 5 times daily  47% of Americans say Facebook is the top influencer of their buying decisions On average, Americans spend %16 of each online hour on Facebook. 70% of marketers acquire new customers through Facebook. And Twitter: Now has over 550 million registered users and 215 million monthly active users Between 2012 and 2014, Twitter achieved a growth rate of 44% 34% of marketers use Twitter for lead generation (Romeri, 2014).† The vast amount of internet users speaks for itself. OXO is conducting business via internet and attracting a multitude of clients through social media and word of mouth. OXO has raised the bar for the kitchen gadget market with its Good Grips product line and its guarantee of satisfaction. They’ve even taken it a step further to cut advertising costs by advertising through social media sites and even creating a blog site in order to listen and respond to consumer thoughts and concerns on their products. References Corporate Design Foundation. (n.d.). Getting a Grip on Kitchen Tools. Retrieved from Corporate Design Foundation: http://www.cdf.org/issue_journal/getting_a_grip_on_kitchen_tools.html Kotler, P., & Armstrong, G. (2014). Principles of Marketing. Upper Saddle, New Jersey: Pearson Education, Inc. OXO. (n.d.). Blogger Outreach. Retrieved from OXO: http://www.oxo.com/bloggeroutreach/ OXO. (1990). Our Roots. Retrieved from OXO: http://www.oxo.com/OurRoots.aspx OXO. (1990). Satisfaction Guarantee. Retrieved from OXO: http://www.oxo.com/Satisfaction.aspx Romeri, M. J. (2014, February 18). New Social Media Statistics You Need to Know. Retrieved from Social Media Today:

Marketing Blog Example

Marketing Blog Example Marketing Blog – Article Example Pricing Strategy Pricing Strategy Given the different demographic characteristics of consumers in the market, marketers are normally faced with difficult situations when they want to make prices for every consumer in the market. For this reason, there is a high tendency by the marketers to group consumers into different segments using the different consumer characteristics, hence coming up with different segments of customers, sometimes known as market segments (Salin, 2012). After a market has been divided I to different segments, there is need to differentiate the products into different forms and sizes that will meet the needs of different market segments. This therefore calls for product differentiation to fit every consumer’s needs. Differentiation makes products to be in different forms and sizes, hence, different prices will apply. In real life, Coca Cola products in the city centers are normally sold in big sizes of containers such as of 10liters, 5 liters, or 2 liters . However, in the remote villages, one will only find these products being sold in small sizes such us in 1 liter, 500ml, 300ml or even smaller quantities. This phenomenon does not just happen by chance, but through critical pricing strategies by marketing managers. Marketing managers have divided the market into segments and identified that consumers in the city centers have a lot of disposable income, hence purchase in bigger quantities. However, the consumers in the villages may be having no or little income, hence can only be able to purchase in smaller quantities. These differences in quantities also have differences in prices tied to them. ReferenceSalin. (2012). Pricing Strategy. Economic Times , 1-2.