Leadership Analysis Summary

The motor vehicle industry in the US has experienced several challenges in the last decade. Several car manufactures in the US have experienced a reduction in revenues due to increased competition in the market. One of the most remarkable leaders in the industry has been Allan Mulally, the President and CEO of Ford Motor Company.Advertising We will write a custom essay sample on Leadership Analysis Summary specifically for you for only $16.05 $11/page Learn More He became the President of the company in 2006 after serving as President of Boeing for several years. He is a qualified aero-nautical engineer and a trained manager. Mulally is a member of several aero- nautical professional associations because of his involvement in the aviation industry. He spent more than 30 years at Boeing, where he served as the firm’s President. He has sat on several boards of aviation associations which made him ideal for the leadership role at Ford Motor Company. The media industry has experienced a lot of changes in the past three decades. Television broadcasting and advertising have had a remarkable influence on many commercial trends across the world. In the US, cable television broadcasting has grown to become a a large industry with various competing firms. These broadcasting firms have their own specialty content which they provide to subscribing viewers. The advertising industry has also developed to become a large industry because of the effect of billboards and other forms of outdoor advertising. One person who is recognized for his role in developing broadcast media in the US, is Ted Turner. Turner is credited with contributing positively to the growth of cable television and outdoor advertising in the country. As a leader, he is keen on trends that change the industry and this can be seen in the way he transformed CNN, TCM, TNT and Cartoon Network. Alan Mulally has initiated several changes in the organizational culture of Ford, a fter becoming CEO in 2006. When he became CEO, the firm was on the verge of being declared bankrupt and had recorded a loss of more than 12 billion dollars, which it had never experienced before. The firm was not able to compete against European and Japanese car manufacturers, which were producing better car models at a lower cost.Advertising Looking for essay on business economics? Let's see if we can help you! Get your first paper with 15% OFF Learn More This problem was also faced by other US car makers because they lacked a competitive advantage in the car market. His background in management helped him to change the way the firm conducted its processes and this improved its performance in the market. He changed the organizational culture in the company which had been severely affected by disunity and internal wrangles among several unit managers. Mulally was able to unite his workers to a common purpose, which made them more dedicated to their duties. The media i ndustry is dominated by several joint conglomerates which have stakes in different television, radio and print companies. This has made some savvy businessmen to increase their influence in the media industry, which has made several media companies across the world to become more powerful. One of the most influential media owners in the world is Ted Turner. Turner is a media mogul who owns CNN, TCM, TNT and Cartoon Network. He is also a recognized philanthropist who participates in various charitable events. Turner has uses his influence to bond with employees in several locations, which has made them have positive attitudes to work. He has managed to exhibit visionary leadership skills which have set him apart from other leaders in the industry. Mulally’s transformational leadership helped Ford register positive performance in the market. Mulally created a new vision for the company which helped to improve its competitiveness in the market. The firm’s employees suppor ted this new vision which helped the firm to benefit from new innovative work practices. This increased the value proposition of Ford car models in the market. This is because the firm’s research and development teams were given the autonomy to use their own creativity to come up with compelling vehicle designs. Mulally managed to increase the competitiveness of Ford’s models in the market, which was dominated by low cost cars manufactured in Asia and Europe. Ford’s employees were able to produce innovative car models which have more powerful engines and consume smaller amounts of fuel. This approach has made it possible for the company to raise its profile in the market.Advertising We will write a custom essay sample on Leadership Analysis Summary specifically for you for only $16.05 $11/page Learn More Ted Turner is a leader who shapes trends in the market. He was able to start billboard advertising in the 1960’s, an idea t hat brought him a lot of profits. He was able to predict that more viewers were interested in cable television in the early 1980’s. Turner has always been involved in all major decisions which are made by his managers. This has made it easy for him to influence employees to have positive attitudes to work. He does not conform to normal industry practices but sets his own standards, which have helped him to be successful in business. He shares with his employees what he wants them to achieve, which makes them set personal goals whenever they perform different tasks. This essay on Leadership Analysis Summary was written and submitted by user Jordan Rivers to help you with your own studies. You are free to use it for research and reference purposes in order to write your own paper; however, you must cite it accordingly. You can donate your paper here.

Quotes from Emperor Justinian I

Quotes from Emperor Justinian I The emperor Justinian I was a formidable leader in 6th-century Byzantium. Among his many achievements is a legal code that would influence medieval law for generations. Here are some quotes from The Code of Justinian, and some that have been attributed to him. The Code of Justinian Those things which seem to many former Emperors to require correction, but which none of them ventured to carry into effect, We have decided to accomplish at the present time with the assistance of Almighty God; and to diminish litigation by the revision of the multitude of constitutions which are contained in the Three Codes; namely, the Gregorian, the Hermogenian, and the Theodosian, as well as in those other Codes promulgated after them by Theodosius of Divine Memory, and by other Emperors, who succeeded him, in addition to those which We Ourselves have promulgated, and to combine them in a single Code, under Our auspicious name, in which compilation should be included not only the constitutions of the three above-mentioned Codes, but also such new ones as subsequently have been promulgated. - The First Preface The maintenance of the integrity of the government depends upon two things, namely, the force of arms and the observance of the laws: and, for this reason, the fortunate race of the Romans obtained power and precedence over all other nations in former times, and will do so forever, if God should be propitious; since each of these has ever required the aid of the other, for, as military affairs are rendered secure by the laws, so also are the laws preserved by force of arms. - The Second Preface For true and pious reasons, We direct that no one shall be permitted to remove from the holy churches persons who take refuge there, with the understanding that if anyone attempts to violate this law, he shall be considered guilty of the crime of treason. - TITLE XII If (as you allege), you, a minor of twenty years of age, have manumitted your slave, although you may have been fraudulently persuaded to do so, still, the imposition of the rod by which freedom is lawfully bestowed cannot be rescinded under the pretext of defect of age; the manumitted slave, however, must indemnify you, and this should be provided for by the magistrate having jurisdiction of the case to the extent that the law permits. - TITLE XXXI It was in your husbands power, in a fit of anger, to change the provisions which he had made in his will with reference to his slaves, namely, that one of them should remain in perpetual servitude, and that the other should be sold in order to be taken away. Hence, if afterwards, his clemency should mitigate his anger (which, although it may not be proved by documentary evidence, still, nothing prevents its being established by other testimony, especially when the subsequent meritorious conduct of the said slave is such that the wrath of the master has been appeased), the arbitrator in the action in partition should comply with the last wishes of the deceased. - TITLE XXXVI It is customary to come to the relief of persons who have attained their majority, where divisions of property have been made through fraud or deceit, or unjustly, and not as the result of a decision in court, because in bona fide contracts whatever is established to have been done unjustly shall be corrected. - TITLE XXXVIII Justice is the constant and perpetual wish to render to every one his due. - Institutiones, Book I Quotes That Have Been Attributed to Justinian Frugality is the mother of all virtues. Glory to God who has thought me worthy  to finish this work.  Solomon,  I have outdone you. Keep cool and you will command everyone. Rather let the crime of the guilty go unpunished than condemn the innocent. Safety of the state is the highest law. The things which are common to all (and not capable of being owned)  are:  the air, running water, the sea and the seashores.

Forensics, Health And Ethics Essay Example | Topics and Well Written Essays - 1250 words

Forensics, Health And Ethics - Essay Example From this article, it is clear that authorities have the upper hand towards what the corpse might be put into. There would be institutions who would honor legal documents while some would need other supporting documents that families would need to satisfy. With regards to ethics, there are still undetermined standards and guidelines concerning people who are mentally challenged. This should be the aspect of health care and ethics, even forensics, which should be further expounded by different associations. It is to protect the rights of people with the mental problem yet is still very much alive and has the same human rights as any normal human being. Appelbaum (1997) even stated that â€Å"Violations of moral rules, in fact, are an inevitable consequence of the complexity of life.† When emotions are put into play, balancing the facts and ethics sometimes become impossible. Emotions would weigh too much that it is the ethics that will overrule the facts which would create conflicts. Some might even go into extremes just to prove their point even if it is not feasible most of the times. People have lost their loved ones and others have lost their careers by not being able to balance facts and ethics properly. However, for some, it is the facts that are weighed more and unethically make decisions. The latter occurs not much as the prior scenario. There should be a different code of ethics for each branch of health science and healthcare. Answering to the needs of people in different situations would mean different judgments to be considered.

Gays should have the same rights as married couples Assignment

Gays should have the same rights as married couples - Assignment Example In America, gay rights have become a central battle in their culture because of the growing acceptance of homosexual relationships that has led to direct threat to dominant Christian norms regarding sex and sexuality. Many people accept marriage as being a union between heterosexuals and this begs the question to define sexes. There are those who define marriage as a religious rite, hence legalizing gay marriage will constitute sacrilege of some level and state intrusion to religious matter. It is untrue to state, and undemonstratable that gay marriage is harmful; on the contrary, gay marriage may benefit us in several ways. Arguments for and against Gay Marriage Marriage between two people who love each other is essential in providing physical and psychological benefits. Research was carried out and it found out that preventing gay couples from marrying might result in psychological problems. When these couples get married, they get access to social support that is essential in faci litating and strengthening heterosexual marriages with the help of psychological and psychical benefits that are associated with that support. Alternatively, gay unions accelerate assimilation of gay couples to a mainstream of heterosexual cultures, which can seize to exist if the gap resent between the experience witnessed between gay and heterosexual is reduced. There are varieties of means that has been used to suppress people who are against same sex marriage (Corvino and Gallagher, 2012). Marriage is therefore, summarized as a means of adopting heterosexual form of family while giving up gay families as well as gay cultures. Majority of gay couples insist the absence of a thing known as traditional marriage, and with the prevalence of both modern and ancient family examples that were nuclear, polygamous, community child rearing, concubines, mistresses, prostitution, etc. are among the unnatural evolutionary thoughts. In comparison, most marriages currently are threatened by hig h rates of divorce. Research carried out in 2008 suggested that 40% to 50% of marriages end up in divorce while 40.6% of babies currently born are born by single mothers; therefore, gay marriage should be banned to prevent weakening of marriage institution. The constitution, by trying to reinforce both equality and liberty to its citizens has given protection to gay couples. This was evident in 1974 when the case of Cleveland vs LaFleur where the verdict given by the court was to declared marriage as personal choice of a person. Vaughn Walker who was a US District Judge wrote on 4 August 2010 that Prop.8 in the state of California that bans gay marriage was not constitutional under the Due process Clause. Another argument against gay marriage is that it leads to slippery floor that will end up giving people polygamous, bestial, among other relationships that are not traditionally recognized an opportunity to marry one another. Glen Lavy, a senior counsel wrote on the 28th day of May 2008 about polygamy movement posing to take advantage of the success of homosexual relations to springboard de-institutionalization of marriage. Another reason gay couples demand their rights to have marital benefits similar to heterosexual couples is that by denying them the right to marry stigmatizes the gay families as being inferior as well as the act of discriminating these type of family as acceptable. Supreme Court

Exploring the nature of the Postmodern Essay Example | Topics and Well Written Essays - 1000 words

Exploring the nature of the Postmodern - Essay Example This transformation has seen the coming and passing of several seasons and eras which have always been defined by particular aspects of life. Modernism and modernity as periods in life were very instrumental in shaping up the destiny and the manner of life in the ages they erupted. It is imperative to realize that such changes basically commence by transforming the mindset of humanity before progressively changing other aspects of life like culture, art, education and sport. In this transformational timescale, the latest era is the postmodern. Postmodernism has totally transmogrified the entire mannerisms and tenets that defined humanity in the earlier epochs. However, inasmuch as postmodernism is meant to be a solution to the basic concept of life, several arguments abound whether it has really been a positive trend it was meant to be. This certainly arises owing to the many issues that surround postmodernism and the several reservations and doubts raised by critics and cynics. That certainly begs the analysis of the whole concept of postmodernism to determine whether these doubts are justified and more importantly to seek into ways and means of making postmodernism an accepted agenda amongst all and sundry. No era in human civilization did transform the world more than modernity and modernism. When postmodernism gradually replaced modernism, its most notable characteristic was its subsequent attack of modernism. In a way, postmodernism is a formulated and calculated move that seeks to debase and criticize the components propounded in modernism. Postmodernists will always seek to find fault in the conventional ways of doing things and in most cases will not submit their solutions or alternatives even after negatively trashing the existing state of affairs (Featherstone, 1995). Postmodernism pervades all sectors of human life including culture, sport, sex, education, philosophy, literature etc .Most importantly, postmodernism if a function of the human

Strategies for Small Molecule Activation

Strategies for Small Molecule Activation Introduction Developing novel strategies for small molecule activation is the core aim of catalysis reasearch. One approach that recently gained prominence in catalytic activation of organic molecules is photoredox catalysis. Visible light photoredox catalysis has risen to the interface of current organic chemistry as a remarkable way to facilitate single electron transfer (SET) processes with organic substrates upon photoexcitation1. This technique relies on the property of metal complexes and organic dyes to undergo SET with visible light2. The commonly employed transition metal based photocatalyst used to harness the packets of energy carried by visible light are polypyridyl complexes of ruthenium and iridium, named as tris(2,2-bipyridine)ruthenium (II) or Ru(bpy)32+ (Figure 1). Figure 1. Structures of common transition metal photocatalysts. These complexes give stable, long-lived excited states (for Ru (bpy)32+*, à Ã¢â‚¬Å¾ = 110 ns)3 when irradiated with visible light of electromagnectic spectrum4. This relatively long lived excited state may allow bimolecular electron-transfer reactions through outer sphere transfer, both by the quenching of excited state photocatalyst and deactivation pathways5. The quenching can be accomplished in both oxidative and reductive ways (Figure 2), which offers this mode of catalysis flexibility. Figure 2. Oxidative and reductive quenching cycles within photocatalysis. Moreover, varying the metal (Ru, Ir, Cu, Cr,etc.) or ligands steer to foreseeable changes in redox potentials, enabling customization of the catalyst to ones needs. In contrast to classical approaches these photochemical methods offer surprisingly mild conditions to radical reactions, as they typically operate at ambient temperature, utilize bench-stable reagents and display high degree of functional group tolerance.6 The extensive application of visible light photocatalysts have been recognized in the field of inorganic and materials chemistry. In particular, these catalysts have been found to be actively decomposing water into hydrogen and oxygen7 and reducing carbon dioxide to methane.8 Also, they have been employed in (i) as components in dye sensitized solar cells9 and organic light-emitting diodes,10 (ii) in polymerization reactions,11 and (iii) in photodynamic therapy.12 Until recently the reports of using these complexes as photocatalysts in organic synthesis were scarce. Their limited investigation was very surprising, as single electron, radical processes offer   a unique pathway and reactivity to form C-C bond which are complementary to the closed shell, two electron processes.13 In the last decade detailed studies form the Yoons , MacMillan sand Stephensons groups have shown the application of Ru(bpy)32+ as photoredox catalyst to perform crucial C-C bond forming reactions such   as [2+2] cycloaddition,14 ÃŽÂ ±-alkylation of aldehydes15 and reductive dehalogenation of activated aryl halides.16 These quality work of above groups have   rejuvenated the interests of many researchers in this field, triggering the diverse ideas into the utility of photoredox catalysis as conceptually novel approach to synthetic organic reaction development. The application of visible light photoredox catalysis in organic synthesis revolves around its ability to engineer unusual bond constructions which are not easily formed by established protocols.   For instance, overall neutral redox reactions can be performed by photoredox catalysis, as both the oxidant and reductants can be generated within the same reaction vessel. Visible light photoredox catalysis has been proved to be convenient in designing reactions, which needs gain and removal of electrons at disparate centres in a reaction mechanism. In contrast to these methods, others require stoichiometric quantity of both oxidant and reductants, which many times are incompatible with each other. Radical intermediates generated from single electron transfer (SET) events have been shown to have different reactivity patterns fundamentally different from those accessed through the ground state of catalyst.17 Harnessing   these intermediates by means other than photoredox cata lysis are often challenging or requires conditions which are incompatible with substrates. It is noteworthy to mention, Ru (II) and Ir (III) based photocatalysts are widely used to generate radicals for use in a diverse range of radical reactions, and most of these reactions occur under mild conditions such as room temperature without the need of reactive radical generators (e.g., azobisisobutyronitrile (AIBN), BEt3), and toxic reagents (e.g., Bu3SnH), and in many cases, high temperature. The source of irradiation typically used are commercially available household light bulbs, which has significant advantage over specialized equipment employing high-energy ultraviolet (UV) light. Moreover, organic molecules generally do not show absorbance in visible region, so there is little probability of unwanted side reactions that might occur from the photoexcitation of the substrate itself. Even, the low photocatalyst loading of 1 mole % or less is sufficient enough to achieve high conversions. These all collectively have proven that visible light mediated photoredox catalysis to b e a uniquely well-suited in designing safer and more sustainable strategies for synthesising more efficient materials and reducing waste streams. Further incentivizing the design and application of novel visible light-mediated methodologies toward both natural and non-natural scaffolds of interest to pharmaceutical and agrochemical domains.18 This review highlights the earlier work done on the use of Ru (II) and Ir (III) transition metal complexes as photoredox catalysts to promote C-C bond forming reactions in organic synthesis. Specifically, there is great emphasis on the applications of visible light photoredox catalysis which have enabled the total synthesis of natural products and related molecules, focusing on a range of powerful transformations that include: reductive coupling, indole functionalization, radical cascades, ATRA reactions, trifluoromethylation and selective C-O bond cleavage. Reductive Dehalogenation Reductive deahalogenation refers to process in which a C-X bond is reduced to a C-H bond where X denotes halogens. These classes of reactions have attracted attention of organic chemists all over the world due to its prime importance in rational organic synthesis. For instance a significant number of examples of these reactions can be found in nature, where enzymatic dehalogenation is performed by microorganism present in soil to check the concentration of lipophilic halogenated species.19 There has been a whole library of reducing systems developed to carry out reductive dehalogenation successfully, which practically guarantees the existence of specific reagents for specific substrate. Organo-tin hydride has been the most used reagent in the past to perform reductive dehalogenation in laboratory as well as in field of synthesis, as it has been proven capable for both radical generation and kinetic radical trapping.20 By far, the system of tin hydride is tributyltin hydride (TBTH) (AIBN) is the most utilized for radical-promoted dehalogenations of organic halides.21 However, there are three main problems in use of TBTH. First, toxicity of tin rule out its use in pharmaceutical synthesis. Second, there are lots of problem associated with the purification of reaction mixture from tributyltin residues. Third, TBTH is not a stable compound, even after careful storage it is likely to steadily decompose.22 It is the toxicity, that has almost precluded its use in a wide range of useful radical reactions in organic synthesis. In recent years, the search for superior alternatives to TBTH has been the central goal of radical chemists. A replacement reagent needs to overcome all three problems mentioned above while at the same time an exhibiting similar reactivity and an ease of use. Earlier work of Fukuzumi and Tanaka focused on use of Ru(bpy)32+ as a photo redox catalyst to promote the reductive dehalogenation of phenacyl bromides23 and reductive dimerization of benzyl bromide24 respectively (Scheme 1), has shown that the application of visible light photoredox catalysis to access radicals can offer a promising solution to this problem. Scheme 1. Reductive dehalogenation of phenacyl bromide (A) and reductive dimerization of benzyl bromide (B). But, it was the efforts of Narayanam and co-workers, focussed on developing the novel means for accessing radical chemistry while avoiding the toxicity and problems associated with tin hydride, has laid a milestone in development of a tin-free reductive dehalogenation systems (Scheme 2.).25 Scheme 2. Photoredox catalytic reduction and potential C-C bond formation. In their primary investigation, Narayanam et al. used a system consisting Ru(bpy)32+ as a photocatalyst, iPr2NEt as major hydrogen atom source and visible light to successfully perform the reductive debromination. In the net transformation, the 3-bromopyrroloindoline (7) was reduced to pyrroloindoline (8) as single product, with the addition of Hantzsch ester or formic acid to the catalytic system produced debrominated product in >90% yield (Scheme 3). Scheme 3. Initial attempt for reductive dehalogenation. In further development of general tin-free visible light mediated dehalogenation protocol, a range of different activated alkyl bromides and chlorides were tested which afforded the corresponding dehalogenated product in good to excellent yield. Although, the un-activated aryl and alkenyl iodides were completely unreactive, as it was expected due to their exceptional negative reduction potentials  Ãƒâ€šÃ‚   (-2.24 V Vs SCE for iodobenzene).26 The solution to this problem lied in the use of Ir(III) based   photo-catalysts instead of   Ru(II), which offered more reducing power than Ru(bpy)32+,and the dehalogenation of less activated alky, vinyl and aryl iodides with good functional group tolerance was achieved using oxidative quencing cycle of fac-Ir(bpy)3 (Scheme 4).27   Scheme 4. Reductive dehalogenation of activated and unactivated halides. Furst et al. used this practical strategy for reductive dehalogenation for a further development of more challenging intermolecular C-C bond forming protocols, which demonstrated an efficient way to promote intermolecular additions using visible light mediated photoredox catalysis. Furst et al. reported a facile coupling of indole with malonate radicals, as malonate-like motifs are common C2-subsitutents in bioactive indole based alkaloids such as actinophyllic acid (9) and undulifoline (10). Using this procedure, an extensive range of indole and pyrrole derivatives were synthesized in good yields by employing (1) as the photocatalyst and N,N-diphenyl-4-methoxyaniline as the reductive quencher (Scheme 5).28 Further, this protocol was extended by Stephenson et al. to synthesize quaternary carbon centres adjacent to C2 of indole based alkaloids by employing more challenging tertiary malonate radicals.29 This transformation was accomplished by directly reducing bromomalonate (11) via oxidative quenching of more reducing fac-Ir(bpy)3 photocatalyst, providing targeted quaternary carbon centres in good to high yields (Scheme 6). Scheme 5. Intermolecular radical addition of secondary radicals to electron-rich heterocycles Scheme 6. Intermolecular radical addition of tertiary radicals to electron-rich heterocycles. Atom Transfer Radical Addition (ATRA) These transformations was first observed by Kharasch30 in 1940s, over the time atom transfer radical addition sparked the interest of organic chemists, as it offers the potential for uniquely efficient and economical approach for dual functionalization of olefins. This functionalization leaved a tremendous impact in organic chemistry, and have also found wide applications in industry and academic research. Similar to the intermolecular malonate-indole coupling mentioned above, these transformations are redox neutral, theoretically eliminating the need for additives, which in terms, reduces the likelihood of deleterious off-target reactivity. The most important application of atom-transfer radical addition reactions is inclusion of fluorinated functional groups into molecules, as the addition of these groups has a strong impact on biological properties and bioavailability of bioactive compounds.31 In 2011 Stephenson, et al. for the first time reported visible light mediated ATRA reactions, proving this methodology as an efficient way to improve the overall performance of this kind of reaction compared to classic radical initiation conditions. This synthetic approach was effective for the preparation of a wide range of perflourohalogenated substrates from unactivated alkenes by using Ru(bpy)32+ as the photocatalyst combined with sodium ascorbate as an electron donor (Scheme 7).32 Scheme 7. Atom transfer radical addition mediated by photoredox catalyst. A similar kind of transformation also providing halotrifluoromethylated product was reported by Han et al. (Scheme. 8)33 using triflouromethanesulfonyl chloride as the triflouromethyl source and visible light in presence of Ru (II) photocatalyst (1). Using this protocol, the variety of substrates including mono, di-, and tri-substituted unactivated alkenes went under trifluoromethylation in excellent yields. Scheme 8. Trifluoromethyl chlorination of disubstituted and internal alkenes. Radical Cascades Radical cascades are one of the most powerful tools for accessing complex structures in single step if substrate is stable under the for radical initiation conditions.34 One of the earliest examples of radical cascade was reported by Stokes et al.35 is intermolecular addition of Sn-radical to alkynes, he also studied the regioselectivity of vinyl radical cyclizations onto C=C double bond (Scheme 9). Cyclization cascades initiated by intermolecular addition of Sn radical to alkyne can be distinguished between reactions where tin-moiety retained in the final product with those where Sn radical essentially acted as a catalyst, which was later removed by the homolytic cleavage of labile C-Sn bond. Scheme 9. Radical cyclization sequence, triggered by regioselective addition of tin radical. Nowadays, because of the recognized toxicity associated with organotin compounds, the focus has been shifted toward the development of alternative tin-free and less environmentally problematic methods for radical cyclizations. Visible light photocatalysis has offered a powerful and sustainable tool for the development of new catalytic radical cascade reactions due their unique ability to facilitate formation of various reactive radicals and radical ions in mild and environmental friendly conditions. Various structurally diverse carbocycles and heterocycles from basic and readily available materials have been synthesis by using this protocol. The augmentation of radical cascade cyclization and visible light photoredox catalysis approach has inspired   radical chemists   around the world to develop novel and efficient methods for synthesis of important heterocyclic motif that are prevalent in nature products exhibiting a wide range of bioactivites. One highly   effective method for radical cascade, generating tetracyclic fused ring was reported by Furst et al. where they used visible light mediated protocol to synthesize tetracycle   from bromomalonate and tricyclic compound from alkyne in good yields as a single diastereomers36 (Scheme 10.). Scheme 10. Intramolecular radical cascades. Xiao et al. further extended the application of visible light mediated radical cascade reactions in synthesis chromam-2ones and dihydroquinoline-2-ones based scaffolds, as these are omnipresent components in biologically active natural products and pharmaceutical drugs37. They reported a new type of radical cascade reaction between photogenerated ÃŽÂ ±-amino radicals and acyloyl ester- and acrylamide-tethered aroylhyrazones.38 (Scheme 11). Scheme 11. Photoredox catalyzed radical cascade reaction of ÃŽÂ ±-amino radicals. In addition, they developed an oxidant free N-radical cascade reaction of ÃŽÂ ², ÃŽÂ ³-unsaturated hydrazones by incorporating visible light photoredox and cobalt catalysis to obtain dihydropyrazole-fused benzosultams (Scheme 12),39 that has never been reported previuosly. Scheme 12. Visible light photocatalytic N-radical cascade reaction of benzosultam synthesis. Recently, Xu et al. devised a valuable cascade annulation by generating acyl radicals from abundant acyl chlorides under visible light mediated photoredox catalysis which then started a cascade cyclization of 1,7 enynes (Scheme 13).40 Scheme 13. Visible light induced cascade cyclization of 1,7-eynes with acyl chlorides. Applications in Total Synthesis In the history of organic synthesis, indole based alkaloids grabbed much more attention because of their abundance in natural products and biologically active compounds, and they have always been interesting and challenging synthetic targets. The unique ability of visible light mediated photoredox catalysis in forming key C-C bond granted access to numerous applied intermediates that facilitated synthesis of these diverse natural products. In 2011, Stephenson and co-workers reported the asymmetric synthesis of (+)-gliocladin C (21), a natural product with interesting cytotoxic activity (Scheme 14.)41 starting from L-tryptophan, the important intermediate C3 bromopyrroloindoline (17) was synthetically prepared by standard transformations using Boc-D-tyrptophan methyl ester (16). The vital step in the synthesis was the formation of C-C coupled intermediate (18), which was accomplished by reductive dehalogenation-arylation process triggered by blue light irradiation on substrate in the presence of aldehyde (22), photocatalyst (1) and NBu3 as a quencher. This intermediate was converted into natural product in 7 high-yielding steps, which was more efficient than the previous reported 21-step structural synthesis of (21) starting isatin with and overall yield of ~ 4%.42 Scheme 14. Total synthesis of (+)-gliocladin C. Another more recent example is the synthesis of biologically active alkaloids drimentines A, F and G (Scheme 15.).43 by Li and co-workers utilising reductive C-C bond forming strategy. In this example, the heterocycle (25) was coupled with acceptor (24) by intermolecular radical 1,4-addition to generate the important intermediate (26), which facilitated the product (27) -(29) in good yields. Scheme 15. Total synthesis of drimentines A, F, G Targeting Pharmaceutically Relevant Scaffolds The unique capabilities of photoredox catalysis is an access to variety of fluoroalkyl radical species at late stage modification of therapeutic leads. Fluorinated functional groups (trifluoromethyl group in particular) have become increasingly popular over the decades44, because these motifs have dramatic on the molecules physiochemical properties, making them more selective, increasing their efficacy, or making them easier to adminster. Photoredox catalysis can provide an approach tailored on industrial scales by using abundantly available CF3 sources and eliminating the need of pre-functionalized substrates. This chemistry was readily translated to multigram scales for a number of substrates, one most important example of this strategy is the synthesis of trifluoromethylated 2-chloropyridine (32) (Scheme. 16) a vital synthon in production of anti-infective agents at Boehringer Ingelheim Pharmaceuticals Inc.45 Scheme 16. Preparation of Boehringer-Ingelheim intermediate. A novel redox system comprising pyridine N-oxide and trifluoroacetic acid was designed by Beatty at el. where C-C activation was achieved by pyridine N-oxide, a redox trigger, which could in situ generate modified trifluoroacetate shifting the redox potential of trifluoroacetate lower, within the reach of Ru(bpy)32+ photoredox catalyst.46 ORL-1 Antagonist Intermediate Opioid receptor-like 1 (ORL-1) antagonist which is currently under the development for the cure of depression and obesity,47 has a gem-difluorobenzyl functional group around the spirocyclic piperidine (34), the earlier synthetic route consisted a total of   8 steps starting from (33) with an overall yield of 28%.48 Futhermore, this sequence included AIBN initiated radical bromination, and most challenging step was the benzylic fluorination by using 2.6 equiv. of Deoxo-Fluor 9 (specialised fluorinated reagent) as a fluoride source, which remained problematic as it required the use of pre-functionalized substrates through classical nucleophilic or electrophilic fluorination. Radical rearrangements reactions have demonstrated the strategic benefits in its synthesis when compared to this method.49 Visible light mediated radical Smiles rearrangement was developed to address the challenging synthesis of gem difluoro group ORL-1 antagonist from fluorinated thiophene (35), which could be produced from difluoro-ethanol from readily available corresponding ethyl ester (Scheme 17) reported by Douglas et al.50 This strategy has solved the problem of high number of steps and overcome the overall low yield and use of specialized fluorinated reagents. This new 5-step synthetic route eliminated the undesirable feature of previous synthetic route, the challenging benzylic defluorination could be accomplished by switching a key transformation to a C-C bond instead of a C-F bond formation. Scheme 17. Previously reported route towards ORL-1 antagonists and new photochemical radical smiles rearrangement route. Biofeedstock Processing Biomass set itself aside from other renewable resources, since the energy it contains is stored in the form of chemical bonds, which allow biomass to be used for several purposes other than generating electricity and heat, such as liquid fuel and value-added chemicals. In particular, depolymerisation of lignin50, one of the most abundant feedstock for aromatic commodity compounds, which has attracted a lot of attention in recent years. Lignin is a stable, branched biopolymer which is a part of the plant cell wall and is primarily responsible for providing rigidity and protection against environmental conditions. Primarily, it is composed of three different types of cinnamyl alcohols coupled together to produce a various array of motifs inside of the polymer chain (Scheme 18). The multiple connectivity and stability has hindered attempts to efficiently isolate value compounds through the degradative processing.51 The most sensible point of start in lignin degradation is ÃŽÂ ²-O-4 linkage, as this is the most abundant (45-65%). Photoredox catalysis provides mild means of cleaving these critical bonds by a two-step procedure, which includes the selective oxidation of the alpha carbon followed by photochemical reductive cleavage.52 Scheme 18. Two steps protocol for degradation of lignin model system. This strategy could be used for efficient degradation of a range of lignin model systems, isolation of the fragmentation products in excellent yields by employing photocatalyst 3 under the reductive quenching conditions. Conclusions. Photoredox catalysis with Ru (II) and Ir (I) metal complexes has recently received widespread attention as a tool for synthetic chemists, and it has been applied to the development of wide range of new C-C bond forming reactions. The utility of photoredox catalysis arises not form its ability to promote C-C bond formation, but rather from its ability to generate a diverse array of reactive via single-electron transfer. As shown, these species include electrophilic ÃŽÂ ±-carbonyl radicals, tert-malonate radicals, ÃŽÂ ±-amino radicals, acyl radicals and trifluoromethyl radicals. These intermediates have been used to develop reactions as varied as reductive dehalogenation, indole functionalization, atom transfer radical additions, radical cascades and Smiles rearrangement. Also, photoredox catalysis has been proved as valuable tool for the synthesis of various biologically active compounds and their derivatives, as demonstrated by its application in the total synthesis of gliocladin C, drimenties A, F, G, and pharma relevant scaffolds. In each of these syntheses, simple and typically inert functionalities in the starting materials are transformed into reactive intermediates upon single electron transfer. These powerful transformations are not only redefining the synthetic strategies, but it has also changed the face of radical chemistry; a fundamental area in organic chemistry which mostly accessible using hazardous radical reagents. These robust class of reactions have inspired many researchers in designing and developing novel approaches to synthetic targets. The growth of visible light phototredox catalysis is not only significant on its own right, also bodes well for the future of organic synthesis. References: Nicholls, T. P.; Leonori, D.; Bissember, A. C., Applications of visible light photoredox catalysis to the synthesis of natural products and related compounds. Natural Product Reports 2016, 33 (11), 1248-1254. James J. Douglas, J. D. N.; Kevin P. C., Enabling Novel Photoredox Reactivity via Photocatalyst Selection. Aldrichimica 2014, 47, 15-25. Kalyanasundaram, K., Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium(II) and its analogues. Coordination Chemistry Reviews 1982, 46, 159-244. Juris, A.; Balzani, V.; Barigelletti, F.; Campagna, S.; Belser, P.; von Zelewsky, A., Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence. Coordination Chemistry Reviews 1988, 84, 85-277. Juris, A.; Balzani, V.; Belser, P.; von Zelewsky, A., Characterization of the Excited State Properties of Some New Photosensitizers of the Ruthenium (Polypyridine) Family. Helvetica Chimica Acta 1981, 64 (7), 2175-2182. Tucker, J. W.; Stephenson, C. R. J., Shining Light on Photoredox Catalysis: Theory and Synthetic Applications. The Journal of Organic Chemistry 2012, 77 (4), 1617-1622. (a) Graetzel, M., Artificial photosynthesis: water cleavage into hydrogen and oxygen by visible light. Accounts of Chemical Research 1981, 14 (12), 376-384. (b) Meyer, T. J., Chemical approaches to artificial photosynthesis. Accounts of Chemical Research 1989, 22 (5), 163-170. Takeda, H.; Ishitani, O., Development of efficient photocatalytic systems for CO2 reduction using mononuclear and multinuclear metal complexes based on mechanistic studies. Coordination Chemistry Reviews 2010, 254 (3-4), 346-354. Kalyanasundaram, K.; Grà ¤tzel, M., Applications of functionalized transition metal complexes in photonic and optoelectronic devices. Coordination Chemistry Reviews 1998, 177 (1), 347-414. Lowry, M. S.; Bernhard, S., Synthetically Tailored Excited States: Phosphorescent, Cyclometalated Iridium(III) Complexes and Their Applications. Chemistry A European Journal 2006, 12 (31), 7970-7977. (a) Lalevà ©e, J.; Blanchard, N.; Tehfe, M.-A.; Morlet-Savary, F.; Fouassier, J. P., Green Bulb Light Source Induced Epoxy Cationic Polymerization under Air Using Tris(2,2à ¢Ã¢â€š ¬Ã‚ ²-bipyridine)ruthenium(II) and Silyl Radicals. Macromolecules 2010, 43 (24), 10191-10195. (b) Fors, B. P.; Hawker, C. J., Control of a Living Radical Polymerization of Methacrylates by Light. Angewandte Chemie International Edition 2012, 51 (35), 8850-8853. Howerton, B. S.; Heidary, D. K.; Glazer, E. C., Strained Ruthenium Complexes Are Potent Light-Activated Anticancer Agents. Journal of the American Chem

Self-Absorption in Hemingway’s A Farewell to Arms Essay -- Hemingway F

Self-Absorption in Hemingway’s A Farewell to Arms Catherine Barkley and Frederick Henry, the main characters in Hemingway’s A Farewell to Arms are two of the most self-absorbed characters I have ever come across. Frederick Henry thinks only of what he wants while Catherine worries only about what Frederick thinks and wants. They are constantly thinking only about themselves, which is why I believe that it was a good thing that the baby was not born alive. They are too absorbed in themselves to think of anyone else. Shortly after meeting Catherine, Frederick attempts to get her into bed. By complimenting her hair, admitting that she had every right to slap him, and holding her hand, he uses these words and actions to get a kiss, the first step towards his goal. He does not stop to think that she might still be grieving for her lost boy and so he should take it slowly. Instead, he plunges right into trying to get her into bed without thinking about how she might feel. When he is hurt and in the hospital, he demands that the nurses pay attention to him although they are not ready for an injured soldier. He gets upset because they do not want to do anything without the doctor’s permission. They were trying to do their job and he just made it more difficult for them. He also did not notice that Catherine was getting tired from working so much. All he saw was that they got to spend time together and so did not think that she might be wearing herself down. It was only with a lot of convincing t hat he finally saw that she needed some time off. Catherine did not even realize herself that she was getting worn down because of how absorbed she was in Frederick. She put his needs and desires before her own and believed that if sh... ...ch other very much, but they did not want to include anyone else in that love. Catherine was more concerned with being a good wife than being a good mother. Frederick just did not seem to think of anything that was not Catherine or himself. They did not think much about the child before it was born and said things like "She won’t come between us, will she? The little brat." "No. We won’t let her." (304). They were too wrapped up in themselves to worry or care about anyone else. If the child had been born alive, it probably would have been neglected or not treated as well as it should be. "Aren’t you proud of your son?" "No, he nearly killed his mother." (325). The hostility that Frederick shows is evident of how the child would have been treated if it had actually lived. Works Cited Hemingway, Ernest. "A Farewell to Arms" Scribner Paperback Fiction, 1929.