bluuebunny/crossref_metadata_2025 huggingface dataset:
The Children Act 1989: Success or failure
Authors: Hornby Simonetta Agnello
Published: November 2020

Heralded as the most progressive legislation of the world, the Children Act of 1989 revolutionized children’s law in England and Wales. It is underpinned by six principles: the supremacy of the child’s interest in all decisions concerning their upbringing and education; the recognition that it is best for any chid to be brought up by their blood family, that his religious and ethnic background must be respected, and that siblings should not be separated; the abolition of the stigma of illegitimacy and its replacement with the attribution at birth of paternal responsibility to the child’s father; the unification of public and private law, and the creation of the ‘menu’ of Residence, Contact, Prohibition, and Specific Issue orders available to the court; the establisment of the new principle that time is of the essence in all cases relating to children; and the creation of the presumption that ‘no order is better than an order’ thus the ingerence of the court must be minimal. I believed in those principles and in the benefits that the Children Act would bring to my clients—children and parents alike. I had some reservations: the system was expensive to implement on two counts: first, it gave the child a ‘guardian’ (a qualified social worker appointed by the court through CAFCASS, a governmental agency), as well as their own solicitor paid for by Legal Aid, as was the representative of the parents, who had the right to instruct independent experts; second, because its requirements of social services and other agencies involved further training and increased resources, as well as further involvement of the judiciary, and increased court time. Hornby and Levy were at the forefront of its implementation: our entire staff received in-house training that was open to other disciplines, within the spirit of cooperation between agencies that permeated the Act and its implementation. I also lectured in Britain and abroad and was proud to tell others that social services were under a duty to keep families united, rather than removing children from parents, and make efforts to return to the family the child removed from it, or if this failed, to place the child within the extended family, or with adoptive parents, within a year.
Preparation for the OSCE Assessment
Authors: Creed Fiona
Published: November 2020

The need to prepare adequately for any university examination is beyond refute and students may struggle with the OSCE assessment if they are unprepared or have unrealistic expectations of the OSCE process (Bloomfield et al. 2010). Adequate preparation will enable you to: ● Minimize any anxiety related to the examination, ● Understand the requirements of the OSCE, ● Facilitate accurate, systematic and timely performance of the OSCE, ● Enable you to give full justice to your professional ability…. OSCEs represent an important opportunity for you to further develop your nursing knowledge and skills. Effective preparation will give you a better opportunity to learn effectively from your OSCE and enable you to view the experience positively (see Chapter 14 Reflecting upon your OSCE). Preparation for your OSCE will clearly be affected by your own learning style and where and how you study is likely to be adapted to suit your own learning needs. You may well have completed a learning style assessment quiz such as Honey and Mumford’s (1986) at university; if not, you are able to access this online. It may be best to link your study for your OSCE to your learning style. Honey and Mumford (1986) identified several differing learning styles that are briefly described here. These include: ● Reflector: Tend to explore issues in depth before reaching a decision, ● Theorist: Logical and enjoy researching and using theory to enable understanding, ● Pragmatist: Like to apply things in practice and experiment with new ideas, ● Activists: Are open to new ideas and learn through experience alongside others. Therefore you can use your understanding of your learning style to help plan how you may best revise/prepare for your OSCE. For example: ● Activist: May prepare best by practising for your OSCE with your colleagues and practising your OSCE in the skills room or in a group outside of university. ● Reflector: May learn best by reviewing your own experience or learning from reflecting on experiences you have had in clinical practice. ● Theorist: May prepare by reviewing the literature and reading around the subject matter of your OSCE in appropriate literature, OSCE and clinical skills books.
Measuring Blood Pressure
Authors: Devis Kate
Published: November 2020

Blood pressure measurements are one part of a circulatory assessment (Docherty and McCallum 2009). Treatments for raised or low blood pressure may be initiated or altered according to blood pressure readings; therefore correct measurement and interpretation of blood pressure is an important nursing skill. Blood pressure should be determined using a standardized technique in order to avoid discrepancies in measurement (Torrance and Serginson 1996). Both manual and automated sphygmomanometers may be used to monitor blood pressure. The manual auscultatory method of taking blood pressure is considered the gold standard (MRHA 2006), as automated monitoring can give false readings (Coe and Houghton 2002), and automated devices produced by different manufacturers may not give consistent figures (MRHA 2006). So, although automated sphygmomanometers are in common use within health care settings in the UK, the skill of taking blood pressure measurement manually is still required by nurses. As a fundamental nursing skill, blood pressure measurement, using manual and automated sphygmomanometers, and interpretation of findings are often assessed via an OSCE. Within this chapter revision of key areas will allow you to prepare thoroughly for your OSCE, in terms of practical skill and understanding of the procedure of taking blood pressure. Blood pressure is defined as the force exerted by blood against the walls of the vessels in which it is contained (Docherty and McCallum 2009). A blood pressure measurement uses two figures—the systolic and diastolic readings. The systolic reading is always the higher figure and represents the maximum pressure of blood against the artery wall during ventricular contraction. The diastolic reading represents the minimum pressure of the blood against the wall of the artery between ventricular contractions (Doughetry and Lister 2008). You will need to be able to accurately identify systolic and diastolic measurements during your OSCE. When a blood pressure cuff is applied to the upper arm and inflated above the level of systolic blood pressure no sounds will be detected when listening to the brachial artery with a stethoscope. The cuff clamps off blood supply. As the cuff is deflated a noise, which is usually a tapping sound, will be heard as the pressure equals the systolic blood pressure —this is the first Korotkoff ’s sound.
Recognition of Acute Deterioration
Authors: Creed Fiona
Published: November 2020

Recognition and prompt treatment of the acutely ill patient is a significant issue in clinical practice (NICE 2007). The need for all nurses to be able to recognize, assess and promptly escalate (ensure timely and effective management) patients whose condition is deteriorating is stressed in the literature (NCEPOD 2005; NPSA 2007). Therefore it is an important skill and your university will want to ensure via OSCE that you are adequately prepared for any emergency that may arise in practice. It must be emphasized that this skill is a complex skill and most universities do not assess this skill until the final year of your course. The key to succeeding in this OSCE is understanding the need for systematic assessment, and timely intervention and escalation will be stressed throughout this chapter. It is likely that you will be allowed approximately half an hour to demonstrate this skill and answer related questions. Revision of key material will enable you to understand why assessment is important and provide you with a systematic framework to use in the OSCE and in clinical practice. Concern over NHS staff ’s management of the deteriorating patient has been highlighted in the literature since the late 1990s. McQuillan et al. (1998) first discussed the concept of suboptimal care suggesting that often deterioration in patients was ignored, misdiagnosed and/or poorly managed in ward environments resulting in increased mortality and morbidity in ward patients. Since McQuillan’s work several other studies have identified similar problems (McGloin et al. 1999; NCEPOD 2005). More recently NICE (2007) has published guidance on recognition and management of deterioration and the Department of Health (2009) has published competencies related to recognition and management of deterioration that all acute staff should achieve. Review of this literature highlights that several issues are clearly important in recognition of acute deterioration and the need to utilize a systematic assessment tool linked to a robust track and trigger scoring system is an important consideration in practice. Smith (2003) was instrumental in developing the ALERT® framework that has been adopted internationally as a robust systematic assessment tool.
Reflecting Upon Your OSCE
Authors: Creed Fiona
Published: November 2020

Once you have completed your OSCE assessment you will be informed of the outcome of the assessment. This may be on the day, if it is a formative assessment, or sometime afterwards, if it is a summative examination that has to be processed through an examination board. You should be provided with detailed written feedback about your performance at the OSCE and it is useful to review this alongside your recollections of the experience as this will help you to learn from the experience. Reflection is an important tool to use whether you have been successful or unsuccessful during your OSCE. It is important in nursing that we are able to reflect and learn from both positive and negative experiences. Some universities may require you to reflect on your OSCE as part of the examination. Again this may be on the day, immediately after your OSCE or a short period afterwards by reviewing a video of your OSCE (the latter normally happening as part of a formative learning process). Reflection is not unique to nurses and is something that we do throughout our lives. In everyday terms reflection may be described as an examination of our personal thoughts and actions (Somerville and Keeling 2004). In nursing you will be encouraged to develop reflective skills to facilitate your learning in the university and in practice this is often referred to as reflective practice and is slightly different to ‘everyday reflection’. Indeed throughout your nursing career you will be encouraged to develop reflective practice skills and become a reflective practitioner. Reflection as a process was first discussed in 1933 by John Dewey who first identified the need to evaluate our experiences and learn from them. In nursing as with most concepts there are a number of definitions of reflection and this can at first appear to be confusing. Simplistically reflection can be defined as a process of examining and exploring an issue that is related to an experience that results in new learning. Therefore reflection refers to a series of steps that you may take to question and explore an experience with the aim of learning from it (Hart 2010).
Missile Deployment: Nucleophilic Substitution
Authors: Atkins Peter
Published: November 2020

The equivalent of a heat-seeking missile in chemistry is a ‘nucleophile’, a lover of nuclei. The ‘missile’ in this case is a special sort of molecule which sniffs out not heat but positive electric charge, the charge of a nucleus glinting through depleted regions of electron cloud in a target molecule. A candidate for such a missile is a negatively charged ion, which can be attracted to the partially exposed positive charge of a nucleus in the target. With nucleus-sniffing in mind, you can perhaps appreciate that if it is possible to blow away some of the electron cloud from the region of a particular C atom in the target molecule, then the nucleophile will home in on that atom and perhaps attach to it. By management of the electron clouds and adroit choice of the incoming missile, therefore, it is possible to build where and what we want. You shouldn’t lose sight of the fact that the ‘missile’ doesn’t just fly through the air and smash into a molecule: it jostles past the solvent molecules, which move aside or sometimes block it and turn it back. When thinking about the reactions in this section, think of the target atom in a molecule as glowing with positive charge and the incoming missile, the reagent, as having an abundance of negative charge spread over at least one of its atoms. The target and missile are drawn together through the solvent, and might snap together, in a manner I shall describe, once they are close to one another. A missile’s successful hunt for a target might then result in reaction and the formation of a new compound. How are the target prepared and the missile launched? One procedure is to go the whole electrical hog and prepare a molecule with a full positive charge on the C atom that has been chosen to be the foundation of the new construction, the proposed site of reaction. The whole hog can be achieved by snipping out an atom that initially is attached to the C atom.
Taking Away: Elimination
Authors: Atkins Peter
Published: November 2020

The hot spots of molecules that I have identified as double bonds (two shared pairs of electrons lying between the same two carbon atoms) and their triple bond cousins are often desirable entities. They are desirable either in their own right or because they can be used in the course of the construction of an elaborate molecule. For instance, a double bond can make the molecule stiffer and resistant to twisting. In Reaction 28 you will see that one particular natural product, quinine, must have a double bond in a particular position for it to be able to function—Nature is very particular about the shape of a molecule that she uses—and the drug’s synthesizers had to find a way to introduce it. How, though, can a double bond be introduced into a molecule that begins life with only single bonds? One approach is ‘elimination’, the expulsion of groups of atoms on neighbouring carbon atoms, leaving those two atoms free to form a second or even third bond to each other. One approach is to pull an H atom (as a proton) or some other group of atoms off one C atom, and then hope that the ensuing convulsions of the electron cloud will result in its accumulation to form a double bond between that C atom and its neighbour. There are two common approaches, one involving an acid and the other a base. Let’s watch what happens when sulfuric acid, 1, is added to 2. The acid, a proton donor, generates H3O+ ions in the usual way by transferring a proton to a neighbouring water molecule and leaving behind an HSO4– ion, and we see one of these ions sidle up to the target molecule. A proton hops across onto the O atom from the H3O+ ion, so forming a positively charged –OH2+ group. There is an immediate convulsion of the electron cloud, and that group escapes as an H2O molecule, leaving behind a positively charged ion with the positive charge mostly localised on the C atom. This ion is unstable but survives briefly.
Seeing the Light: Vision
Authors: Atkins Peter
Published: November 2020

Now for that extraordinary and wonderful sense, vision. A lot of physics and physiology goes on between the object observed and the focus of its image on the retina of the eye, but the interface of the image with the brain is photochemical. About 57 per cent of the photons that enter the eye reach the retina; the rest are scattered or absorbed by the ocular fluid, the fluid that fills the eye and helps to maintain its shape. You need to know that the ‘rods’ and ‘cones’, the physical receptors distributed over the retina, contain a molecule called retinal, 1, which is anchored to a protein, opsin, to give the aggregate known as rhodopsin. Here the primary act of vision takes place, in which that rhodopsin absorbs a photon. Rhodopsin is the primary receptor for light throughout the animal kingdom, which indicates that vision emerged very early in evolutionary history, no doubt because of its enormous value for survival. Incidentally, a retinal molecule resembles half a carotene molecule, one of the molecules that contribute to the colour of carrots, which is why there is an at least apocryphal connection between eating carrots and improving one’s vision. Let’s stand almost literally eye-to-eye and watch what happens when a retinal molecule in your eye absorbs a photon that might have bounced off this page as you read it. I have indicated the shape of the opsin molecule by ribbons which show in a general way where its numerous atoms lie. The photon passes through your pupil, negotiates the ocular fluid, and plunges into the retinal hotspot of rhodopsin. We see it stir up the electron cloud of the long chain of carbon atoms in the tail of the retinal molecule. That stirring briefly loosens the double bond character of the links between the atoms, and the molecule snaps into a new shape with the carbon tail now straight. The storm in the electron cloud subsides and all the bonds are restored, but now the retinal molecule is trapped in its new shape.
Understanding Asthma
Authors: Pearce Linda , Prigmore Samantha
Published: November 2020

The aim of this chapter is to provide nurses with the knowledge to be able to assess, manage, and care for people with asthma in an evidence-based and person-centred way. The chapter will provide a comprehensive overview of the causes, risk factors, and impact of asthma, before exploring best practice to deliver care, as well as to prevent or minimize further ill-health. Nursing assessments and priorities are highlighted throughout, and the nursing management of the symptoms and common health problems associated with asthma can be found in Chapters 15 and 22, respectively. In the absence of a standardized definition of asthma, it is accurately described as:…Airway inflammation and hyper-responsiveness characterised by widespread reversible narrowing of the airways, which varies either spontaneously or in response to treatment. (British Thoracic Society/Scottish Intercollegiate Guidelines Network, 2009)…The clinician diagnosis of asthma is based on symptoms, patient history, lung function testing (including peak expiratory flow rate diary), and the demonstration of an efficacious response to a trial of inhaled therapy. An estimated 5.4 million people in the UK are receiving treatment for asthma (Lung and Asthma Information Agency, 2006). In 2006–07, there were 67,077 hospital admissions for asthma in England, over 40% of which were for children under the age of 15 (Asthma UK, 2010). Asthma is estimated to cost the NHS £1 billion per year. With one in five households affected, asthma accounts for at least 12.7 million workdays lost each year (Asthma UK, 2005). In 2008, there were 1,071 deaths in England and Wales due to asthma (Office for National Statistics, 2009). Atopy is a genetically based condition in which individuals have a tendency to hypersensitivity in their reaction to allergens and other triggers. The reaction is usually immediate and localized, and manifests in diseases such as asthma, hay fever, and contact dermatitis. Genetic studies (Holloway et al., 2010) investigating atopy and asthma have shown linkages to many chromosomal locations indicating genetic heterogeneity (having different characteristics and qualities). There is genetic control over the ability to produce significant quantities of immunoglobulin E (IgE), a blood plasma protein that activates allergic reactions by acting as an antibody, when exposed to environmental allergens.
Surgical Anatomy of the Ocular Adnexa
Authors: Jordan David , Mawn Louise , Anderson Richard L.
Published: November 2020

Surgical Anatomy of the Ocular Adnexa is a beautifully and thoughtfully illustrated anatomical text that provides the ophthalmic surgeon or any surgeon working in the eyelid/orbital region with detailed yet concise, easy to read and understand descriptions of the anatomy in any particular region of the eyelid, orbit or nasolacrimal system. Throughout the text are clinical pearls and vignettes to help the reader appreciate why certain anatomical features are important to understand. Key anatomical concepts are highlighted and easy to visualize with real cadaver photos as well as the artists rendition of the same region. This book: - Develops a thorough understanding of the anatomy in the eyelid, orbit, nasolacriaml and periocular regions. - Fosters an appreciation of how knowledge of the anatomy leads to a better understanding of the pathophysiology of various disease processes involving the eyelid, orbit, nasolacrimal and periocular region. - Conveys the importance of anatomy in the surgical approach to various disease processes in the eyelid, orbit, nasolacrimal and periocular regions. This second edition will be an invaluable guidel to all those working in the eyelid, orbital, and nasolacrimal areas including residents, fellows and staff in ophthalmology, otolaryngology/head and neck surgery, plastic surgery and neurosurgeons working in and around the orbit.
How Should Chemists Think?
Authors: Hoffmann Roald
Published: November 2020

The Vatican holds a fresco by Raphael entitled The School of Athens. Plato and Aristotle stride toward us. Plato’s hand points to the heavens, Aristotle’s outward, along the plane of the earth. The message is consistent with their philosophies—whereas Plato had a geometric prototheory of the chemistry of matter, Aristotle described in reliable detail how Tyrian purple (now known to be mainly indigo and dibromoindigo) was extracted from rock murex snails. Plato searched for the ideal; Aristotle looked to nature. Modern chemistry faces the quandary that Raphael’s fresco epitomizes. Should it follow the hand sign of Aristotle or that of Plato? Is nature as fertile a source for new materials as some assert it to be? Can we, for example, hope to make better composites by mimicking the microstructure of a feather or of a strand of spider’s silk? Are chemists better advised to seek their inspiration in ideal mathematical forms, in icosahedra and in soccer balls? Or should we hazard chance? To some, the division between natural and unnatural is arbitrary; they would argue that man and woman are patently natural, and so are all their transformations. Such a view is understandable and has a venerable history, but it does away with a distinction that troubles ordinary and thoughtful people. So I will distinguish between the actions, mostly intended, of human beings and those of animals, plants and the inanimate world around us. A sunset is natural; a sulfuric acid factory is not. The 1.3 billion head of cattle in this world pose an interesting problem for any definition. Most of them are both natural and unnatural—the product of breeding controlled by humans. The molecules that exist naturally on the earth emerged over billions of years as rocks cooled, oceans formed, gases escaped, and life evolved. The number of natural molecules is immense; perhaps a few hundred thousand have been separated, purified, and identified. The vast majority of the compounds that fit into the unnatural category were created during the past three centuries. Chemists have added some 70 million well-characterized molecules to nature’s bounty.
Specific Learning and Teaching Strategies That Work, and Why They Do So
Authors: Hoffmann Roald , McGuire Saundra Y.
Published: November 2020

The two of us have been teaching and helping others to teach chemistry at every level—from high school teachers to undergraduate and graduate students to university faculty—for over four decades. From that experience have come a number of teaching and learning tactics that we find effective in facilitating student learning. Initially improvised, these strategies are more than gimmicks, for they have proven themselves in practice. Here we share some of them. Since we are inclined to be reflective as well as pragmatic, we’ve also sought out in recent advances in cognitive psychology, and in the scholarship of teaching and learning, insight into why these approaches work. We think through why they are of use in those most magical and mystical processes of learning and teaching any subject, not just chemistry. And we also spell out potential problems. Caring deeply for student learning entails keeping an eye out for what works for others. Perforce, this means borrowing and adapting. Thus a potential injustice in our account is that credit may not be given to the real innovators. Frankly, we do not know where some of the strategies we suggest originated—in examples by others, or out of our own improvisations as we struggled to become better teachers. Many people have independently come to similar practices. Some of what we write is addressed to teachers, some to students. This is deliberate. Cognizance of learning strategies benefits teachers, and awareness of teaching strategies can help learners understand the motives of teachers. Teaching and learning are a double flame. Take notes by hand, even if the class notes are being provided by the instructor or a for-profit service. Even if they are web-cast. Preferably not later than the evening of the class day, rewrite your notes, by hand, amplifying their content. Notice that this process involves two stages—taking the original notes and then rewriting/reworking them. There are various note-taking systems, including the Cornell Note Taking System, the mapping method, the outline method, etc., that students can learn.
Science and Ethics: A Marriage of Necessity and Choice for This Millennium
Authors: Hoffmann Roald
Published: November 2020

Think of the last two hundred years. Incredible things were given to us by other human beings, in art, music, and social structure—who will question the value of War and Peace, or a Cezanne painting, a Beethoven quartet. Or the end of slavery, the empowerment of women. One should not compare the incommensurate, but there is no question that among the greatest achievements of these years is the gain in our understanding of the world within us and around us, the outcome of science. The achievements of science are of value to humanity in material and spiritual ways. Our own chemistry has so much to be proud of—the extension of life expectancy from forty years to seventy (in part of the world), birth control, synthetic fertilizers to feed twice as many people as could have been fed before, chemotherapy, synthetic fibers and plastics with their myriad of uses, a greater color palette for all. Science, coupled with technology, is democratizing in the deepest sense of the word—it makes available to a wider range of people the necessities and comforts that in a previous age were reserved for a privileged few. The achievement is also spiritual. I am not talking only about the indirect benefit of being able to hear Bob Marley and the Wailers, or a raga, Sind Bhairavi, on a CD. Anywhere in the world. I speak of the direct spiritual value, of knowledge gained of how genetic information is transmitted, stars are born, or how the color of a cornflower comes about. A knowledge that may not be of material value, will not make millions, but still makes the human spirit soar. Given this incredible gain in our knowledge, and the ever-so-clear material improvements in our life span and comfort (and that of much, not nearly all, of the world as well), it is clear as we stand at the beginning of the 21st century that (a) people are not any happier than they were, say, 100 years ago. And (b) that many do not praise the achievements of science and technology with enthusiasm, but question them. Or are suspicious of them.
The Material and Spiritual Rationales Are Inseparable
Authors: Hoffmann Roald
Published: November 2020

There are sound spiritual reasons for the ecological and environmentalist perspective—for minimizing pollution and harm to ourselves, to future generations, to the earth. Are these consistent with the material reality and aspirations of chemistry and chemical industry? One would like to think they are. But what of the realities? I want to take a hard, personal look at this fundamental tension. And also search for what is special about Green or Sustainable Chemistry, facing up to the obstacles confronting the field. And, while reaching for a measure of transformation, a multifaceted Green Index, to come back to a moral perspective on our creative activities. Chemists and chemical engineers are prone to believe that the general public does not recognize the contributions that chemistry has made to our health and our standard of living. And we often cringe at the perception that others blame us (and the great industries that employ us) for fouling our own nest, the infinity of ways we have found of affecting adversely our bodies and the earth by producing on the megaton scale the unnatural. Each of these adverse opinions can be productively discussed—both with the people whose adversarial or anguished arguments chemists react to, and with the chemists’ exaggerated and defensive response to them. The facts remain that the industries that transform matter (to which chemistry is central) have flourished to an extent that is staggering. They’ve played an essential material role in prolonging life, and while not making people any happier, they have provided spiritual value. The value I’m thinking of is not in creating the materials for CDs and books, ancillary tools to spiritual satisfaction, but in providing partial, yet unprecedented knowledge of the world. And the transformative industries are also responsible for an immense quantity of hazardous waste. The scale of their fecund creative enterprise is such that the major cycles of the world are perturbed. More than half the N and S atoms in our bodies have seen the inside of a chemical factory. And C, O, and H atoms too, through agriculture, food preparation, and sewage treatment.
New Methods for Functional Group Conversion
Authors: Taber Douglass
Published: November 2020

Ilya M. Lyapkalo of the Academy of Sciences of the Czech Republic, Prague, showed (Synlett 2009, 558) that a ketone 1 reacted with the inexpensive nonaﬂuorobutanesulfonyl ﬂuoride in the presence of a phosphazene base to give first the enol sulfonate, and then the alkyne 2. The method worked well for aldehydes also. Christophe Darcel of the Université de Rennes I developed (Adv. Synth. Cat. 2009, 351, 367) an inexpensive Fe catalyst for the hydration of a terminal alkyne 3 to the ketone 4. Carlos Alonso-Moreno and Antonio Otero of the Universidad de Castilla-La Mancha devised (Adv. Synth. Cat. 2009, 351, 881) a Rh catalyst for the complementary hydration of a terminal alkyne 5 to the aldehyde, by way of the imine 7. Internal alkynes often give mixtures of ketones on hydration, but Bo Xu and Gerald B. Hammond of the University of Louisville found (J. Org. Chem. 2009, 74, 1640) a gold catalyst that converted an alkynyl ester 8 into the γ-keto ester 9. Jonathan M. J. Williams of the University of Bath developed (J. Am. Chem. Soc. 2009, 131, 1766; Tetrahedron Lett. 2009, 50, 3374) a Ru-catalyzed protocol for the alkylation of an amine 11 with an alcohol 10 . The reaction proceeded by oxi dation of the alcohol to the aldehyde, imine formation, and reduction using the hydride generated by the initial oxidation. José Luis García Ruano of the Universidad Autónoma de Madrid uncovered (Chem. Commun. 2009, 404) a similar conversion mediated by Raney Ni. There has been a great deal of work recently on the preparation and reaction of amides. Susumu Saito of Nagoya University prepared (J. Am. Chem. Soc. 2009, 131, 8748) a diaryl boronic acid that catalyzed the methanolysis of an imide 13 to the methyl ester 14 and the oxazolidinone 15. Jaume Vilarrasa of the Universitat de Barcelona reported (J. Org. Chem. 2009, 74, 2203) the catalyzed condensation of an acid 16 with an azide 17 to give the amide 18 . Both aryl and aliphatic azides participated in the reaction, and the enantiomeric integrity of the amide was maintained.
C-H Functionalization to Form C-O, C-N, and C-C Bonds
Authors: Taber Douglass
Published: November 2020

A classic example of C-H functionalization is the familiar NBS bromination of a benzylic site. Recent updates of this approach allow for direct alkoxylation (J. Am. Chem. Soc. 2008, 130, 7824) and net amination (Organic Lett. 2008, 10, 1863). For the amination of simple aliphatic H’s, Holger F. Bettinger of Ruhr-Universität Bochum developed (Angew. Chem. Int. Ed. 2008, 47, 4744) the boryl azide 2. The insertion with 1 proceeded to give a statistical mixture of the nitrene insertion products 3 and 4. The tethered C-H functionalization devised (J. Am. Chem. Soc. 2008, 130, 7247) by Phil S. Baran of Scripps-La Jolla is selective, as in the conversion to 5 to 6, but appears to be limited to tertiary and benzylic C-H sites. Michael P. Doyle of the University of Maryland established (J. Org. Chem. 2008, 73, 4317) an elegant protocol for the oxidation of an alkyne such as 7 to the ynone 8. Note that the oxidation did not move the alkyne. Marta Catellani of the Università di Parma reported (Adv. Synth. Cat. 2008, 350, 565) the intriguing Pd-catalyzed conversion of 9 to 10. Under mild conditions, it might likely be possible to hydrolyze the vinyl ether to reveal the phenol 11. Another way of looking at this overall transformation would be to consider the ether 10 to be a protected form of the aldehyde 12. C-H activation can also lead to C-C bond formation. Irena S. Akhrem of the Nesmeyanov Institute, Moscow, described (Tetrahedron Lett. 2008, 49, 1399) a hydride-abstraction protocol for three-component coupling of a hydrocarbon 13 , an amine 14 , and CO, leading to the homologated amide 15. Hua Fu of Tsinghua University, Beijing, showed (J. Org. Chem. 2008 , 73, 3961) that oxidation of an amine 16 led to an intermediate that could be coupled with an alkyne 17 to give the propargylic amine 18. Products 15 and 18 are the result of sp2 and sp coupling, respectively. C-H functionalization leading to sp3 -sp3 coupling is less common. Jin-Quan Yu of Scripps/La Jolla found (J. Am. Chem. Soc. 2008, 130, 7190) that activation of the N-methoxy amide 19 in the presence of the alkyl boronic acid 20 gave smooth coupling, to 21.
Developments in Alkene Metathesis
Authors: Taber Douglass
Published: November 2020

Alkene metathesis has been extended to increasingly complex starting materials and products. Nitriles are good donors to coordinatively-unsaturated transition metal centers, so tend to inhibit the reaction. Ren He of Dalian University of Technology has found (Tetrahedron Lett. 2007, 48, 4203) that inclusion of the loosely-coordinating 2-methyl pyridine in the reaction enables facile cross-coupling with acrylonitrile 2. Although crosscoupling with (Z, Z)-sorbate is not efﬁcient, Dennis P. Curran of the University of Pittsburgh has shown (Organic Lett. 2007, 9, 5) that cross-coupling with (E, Z)-sorbate 5 works well. For large scale work, he has developed a Hoveyda-type catalyst with a perﬂuoro tail, that is recoverable in 70% recrystallized yield from the reaction mixture. Shigefumi Kuwahara of Tohoku University has reported (Tetrahedron Lett. 2007, 48, 3163) a practical alternative for direct metathesis to deliver (E, E)-dienyl esters. Continuing the investigation of tandem Ru-catalyzed reactions, Marc L. Snapper of Boston College effected (Organic Lett. 2007, 9, 1749) metathesis with methacrolein 8a, then added Ph3P and diazoacetate, to give the diene 11. A range of common Ru catalysts worked well for this transformation. In an alternative approach to trisubstituted alkene construction, Stellios Arseniyadis and Janine Cossy of ESPCI Paris have demonstrated (Organic Lett. 2007, 9, 1695) that inclusion of Cl-catecholborane 14 allows clean cross metathesis with the lactone 13. The construction of tetrasubstituted alkenes has been more challenging. Yann Schrodi of Materia, Inc. (Organic Lett. 2007, 9, 1589) has described a catalyst 17 that is particularly effective. Complex 17 was superior to a catalyst reported (Organic Lett. 2007, 9, 1339) shortly earlier by Robert H. Grubbs of Caltech. Debendra K. Mohapatra of the National Chemical Laboratory, Pune, and Professor Grubbs, in a new approach to macrocyclic stereocontrol, have made (Tetrahedron Lett. 2007, 48, 2621) the remarkable observation that the cyclization of the bis ether 19a gave 20 in a 9:1 E / Z ratio, while cyclization of the diol 9b gave only Z - 21. Oligomer formation can often compete in such medium ring-forming reactions. Deryn E. Fogg of the University of Ottawa has raised (J. Am. Chem. Soc. 2007, 129, 1024) the cautionary (but happy!) observation that while the cyclization, for instance, of 22 proceeded efficiently to give 23, at an intermediate point in the transformation the product was more than half oligomer.
Developments in Alkene and Alkyne Metathesis
Authors: Taber Douglass
Published: November 2020

Jon D. Rainier of the University of Utah has put forward (J. Am. Chem. Soc. 2007 , 129 , 12604) an elegant alternative to Ru-catalyzed alkene metathesis, demonstrating that an ω-alkenyl ester such as 1 will cyclize to the enol ether 2 under Tebbe conditions. The particular reactivity of free alcohols in Ru-catalyzed alkene metathesis is underscored by the observation (Tetrahedron Lett. 2007, 48, 6905) by Javed Iqbal of Dr. Reddy’s Laboratories, Ltd., Miyapur that attempted metathesis of the ether 4a failed, but metathesis of the diol 4b proceeded efficiently. Kazunori Koide of the University of Pittsburgh has demonstrated (Organic Lett. 2007, 9, 5235) that the yields of cross-metathesis with an alkenyl alcohol could be enhanced by binding it to a trityl resin. He observed that the Grela catalyst 8 was particularly effective in this application. Residual Ru species do not interfere with some subsequent transformations. Rodrigo B. Andrade of Temple University has demonstrated (Tetrahedron Lett. 2007, 48, 5367) that metathesis with an α, β-unsaturated aldehyde such as 11 can be followed directly by phosphonate condensation to give the doubly-homologated product 12. Philip J. Parsons of the University of Sussex has found (Organic Lett. 2007, 9, 2613) that the nitro functional group is compatible with the Ru catalyst. The product nitro alkene 15 could be cyclized (intramolecular Michael addition) to the cyclopentane 16, or (intramolecular dipolar cycloaddition) to the cyclopentane 17. There has been much interest in carrying out the several alkene metathesis transformations (cross metathesis, ring closing metathesis, ring-opening metathesis polymerization) in water. Robert H. Grubbs of the California Institute of Technology has designed (Angew. Chem. Int. Ed. 2007, 46, 5152) the ammonium salt 18 for this purpose, and Karol Grela of the Polish Academy of Sciences in Warsaw and Marc Mauduit of ENSC Rennes have jointly(Chem. Commun. 2007, 3771) put forward the pyridinium salt 19. Remarkably, Ronald T. Raines of the University of Wisconsin has shown (Organic Lett. 2007, 9, 4885) that the Hoveyda catalyst 20 is sufficiently stable in aqueous acetone and aqueous DME to function efficiently.
Enantioselective Preparation of Secondary Alcohols and Amines
Authors: Taber Douglass
Published: November 2020

Secondary alcohols can be prepared in high enantiomeric excess by catalytic hydrogenation of ketones. Zhaoguo Zhang of Shanghai Jiaotong University has established (Organic Lett. 2007, 9, 5613) that β-keto sulfones such as 1 are suitable substrates for this hydrogenation. Reinhard Brückner of the Universität Freiburg has demonstrated (Angew. Chem. Int. Ed. 2007, 46, 6537) that the rate of hydrogenation of β-keto esters such as 3 and 5 depends on the alcohol from which the ester is derived, so 3 can be reduced to 4 in the presence of 5. Enantiomerically-pure secondary alcohols and amines can also be prepared by adding an oxygen or a nitrogen to an existing carbon skeleton. Both Srivari Chandrasekhar of the Indian Institute of Chemical Technology, Hyderabad (Tetrahedron Lett. 2007, 48, 7339) and Arumugam Sudalai of the National Chemical Laboratory, Pune (Tetrahedron Lett. 2007, 48, 8544) have taken advantage of the previously-described enantioselective α-aminoxylation of aldehydes to establish what appears to be a robust preparative route to the enantiomerically-pure epoxides such as 9 of terminal alkenes. Karl Anker Jørgensen of Aarhus University has developed (Chem. Commun. 2007, 3646) a catalyst for the enantioselective addition of 11 to nitroalkenes such as 10. Armando Córdova of Stockholm University has shown (Tetrahedron Lett. 2007, 48, 5976) that epoxy aldehydes such as 14, easily prepared by the protocol he developed, are converted by the Bode catalyst to β-hydroxy esters such as 15. Hyunsoo Han of the University of Texas, San Antonio has described (Tetrahedron Lett. 2007, 48, 7094) an improved protocol for the enantioselective conversion of primary allylic carbonates 16 to secondary amines 17. René Peters of ETH Zurich has used (Angew. Chem. Int. Ed. 2007, 46, 7704) a related procedure for the construction of aminated quaternary centers. Mukund P. Sibi of North Dakota State University has devised (J. Am. Chem. Soc. 2007, 129, 8064) a catalyst for the conjugate addition of the benzyloxyamine 20 to acyl pyrazoles, and Claudio Palomo of the Universidad de País Vasco has found (Angew. Chem. Int. Ed. 2007, 46, 8054) that a simple diphenyl prolinol catalyst will effect enantioselective α-amination of aldehydes.
C-O Ring Natural Products: (-)-Serotobenine (Fukuyama-Kan), (-)-Aureonitol (Cox), Salmochelin SX (Gagné), Botcinin F (Shiina), (-)-Saliniketal B (Paterson), Haterumalide NA (Borhan)
Authors: Taber Douglass
Published: November 2020

Tohru Fukuyama of the University of Tokyo and Toshiyuki Kan of the University of Shizuoka devised ( J. Am. Chem. Soc. 2008, 130, 16854) the chiral auxiliary-directed Rh-mediated cyclization of 1, setting the two stereogenic centers of 2 with high stereocontrol. The ester 2 was carried on to the indole alkaloid (-)-Serotobenine 3. In the course of a synthesis of (-)-Aureonitol 6, Liam R. Cox of the University of Birmingham developed (J. Org. Chem. 2008, 73, 7616) the diastereoselective intramolecular addition of an allyl silane 4 to give the tetrahydrofuran 5. In analogy to what is known about the intramolecular ene reaction, the diastereocontrol observed for this cyclization may depend on the allyl silane being Z. Michel R. Gagné of the University of North Carolina found (J. Am. Chem. Soc. 2008, 130, 12177) that the Ni-catalyzed coupling of organozinc halides could be extended to glycosyl halides such as 7. This opened ready access to C -alkyl and C -aryl glycosides, including Salmochelin SX 10. Isamu Shiina of the Tokyo University of Science established (Organic Lett. 2008, 10, 3153) that the acid-mediated cyclization of the Sharpless-derived epoxide 10 proceeded with clean inversion, to give 11. The highly-substituted tetrahydropyran core 11 was then elaborated to the antifungal Botcinin F 12. Ian Paterson of Cambridge University optimized (Organic Lett. 2008, 10, 3295) the Pd-catalyzed spirocyclization of the ene diol 13, leading to 14, the enantiomerically-pure bicyclic core of (-)-Saliniketal B 15. Haterumalide NA 18 presented the particular challenge of assembling the geometrically-defined chloroalkene, in addition to closing the macrolide ring. Babak Borhan of Michigan State University addressed (J. Am. Chem. Soc. 2008, 130, 12228) both of these challenges together, electing to employ a chlorovinylidene chromium carbenoid, as developed by Falck and Mioskowski, to effect the macrocyclization of 16 to 17.
Organocatalytic Ring Construction: The Corey Synthesis of Coraxeniolide A
Authors: Taber Douglass
Published: November 2020

Armando Córdova of Stockholm University has found (Tetrahedron Lett. 2008, 49, 4209) that the organocatalyst 3a effected enantioselective conjugate addition of bromonitromethane 2 to the α,β-unsaturated aldehyde 1, to give the cyclopropane 4 as a ~ 1:1 diastereomeric mixture, both in high ee. Tomislav Rovis of Colorado State University has published (J. Org. Chem. 2008, 73, 2033) a detailed account of his development of catalysts such as 6, that effected enantioselective cyclization of 5 to 7 with excellent ee. Karl Anker Jørgensen of Aarhus University has employed (J. Am. Chem. Soc. 2008, 130, 4897) chiral quaternary salts derived from quinine that mediated the enantioselective addition of prochiral rings such as 8 to the allenoate ester 9 to give 10 with high ee. Organocatalysts have also been used to prepare more highly substituted cyclohexane derivatives. Guofu Zhong of Nanyang Technological University used (Organic Lett. 2008, 10, 2437) a quinine-derived secondary amine to catalyze the Michael addition of 12 to 11 followed by intramolecular aldol (Henry) reaction, to give 13. When Professor Jørgensen attempted (Angew. Chem. Int. Ed. 2008, 47, 121) the related addition of 14 and 15 using catalyst 3a, he did not observe the expected Michael-Michael sequence. Rather, the initial Michael addition was followed by a Morita-Baylis-Hillman condensation, to give 16. The β-keto ester 16 existed primarily in its enol form. Organocatalysts can also be used to prepare polycyclic systems. Professor Jørgensen has found (Chem. Commun. 2008, 3016) that condensation of 14 with acetone dicarboxylate 17, again using catalyst 3a, gave the bicyclic β-keto ester 18. Matthew J. Gaunt of the University of Cambridge observed (J. Am. Chem. Soc. 2008, 130, 404) that for the cyclization of 19, catalyst 3b was superior to catalyst 3a. The power of desymmetrization of prochiral intermediates was illustrated by the report (J. Am. Chem. Soc. 2008, 130, 6737) from Benjamin List of the Max-Planck-Institute, Mülheim of the cyclization of 21 to 23. Organocatalysts can also be used to prepare larger rings.