bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemists Who Are Leaders in Academia or Organizations
Authors: Brown Jeannette E.
Published: November 2020

Amanda Bryant-Friedrich (Fig. 4.1) is Dean of the College of Graduate Studies at the University of Toledo (Toledo). Amanda was born in Enfield, NC, a small town about fifteen miles from the North Carolina-Virginia border. Her father was a farmer and her mother was a housewife. Her father only had a sixth-grade education and did not read or write much. Her mother graduated from high school in Enfield. Her maternal grandfather was a child of a slave and her mother was one of twenty-two children from two wives. They lived on a farm owned by a man named Whitaker. As her mother’s family had been enslaved by the family that owned the farm, her last name was Whitaker. Amanda’s paternal grandfather was a businessman who owned his own farm, on the other side of town. He was also involved in the illegal production of moonshine. Amanda went to Unburden Elementary School in Enfield. Her first experience with school was dramatic, because she lived at the end of a dirt road and was really isolated from other families. The first day she went to kindergarten she saw all those little kids, and she was afraid because there were too many people there. But the daughter of her mother’s best friend was there and invited her to come in to the classroom. Her first science class was in general science in fourth or fifth grade. She was so fascinated, she changed her mind about her future career of secretary or teacher and decided on science. Amanda went to Enfield Middle school in Halifax County, then the second poorest county in the state. The school had only basic infrastructure for science classes. She remembers her middle school chemistry teacher, Ms. Crowley, who told the students to put a mercury thermometer in a cork and Amanda accidently stuck it in her hand. They did not have much in the school, but her teacher taught her what she could.
Next Steps
Authors: Brown Jeannette E.
Published: November 2020

This book relates the stories of some amazing women who are currently working as chemists or are recently retired. These women, as I have said before, are hiding in plain sight. Perhaps the first or the only woman of color to work in a particular lab or university, they all managed to succeed in spite of any obstacles they faced. This chapter presents some ideas as to what you can do in order to succeed if you, your child, grandchild, or students might be interested in a STEM career, especially in chemistry. I highly recommend reading Dr. Sandra L. Hanson’s book, Swimming against the Tide: African American Girls and Science Education. Dr. Hanson studied young African American girls in high school and their attitudes toward science, which has traditionally been a male profession. One of her conclusions is that these young girls need to see or read about role model, an African American woman chemist. Swimming against the Tide was written before the explosion of the World Wide Web and web-based materials, so this conclusion may no longer hold. For example, information about most of the women in this book is available on the web; some of them have given talks that are also on the web. Many of the women whose stories are told here work to mentor young minority students. These web based materials can be accessed by the students and teachers. The primary organization that focuses on careers in chemistry is the ACS. What is chemistry? It is a branch of science that provides opportunities for a variety of careers, not just working in a research laboratory making new chemicals. According to the ACS, “In simplest terms, chemistry is the science of matter, for example anything that can be touched, tasted, smelled, seen or felt is made of chemicals.” The ACS website has information on chemistry careers, including videos of the different jobs that chemists do, and information on various technical disciplines, as well as profiles of many chemists, including one whose life story is in this book.
The Matrix of Modeling, Mentoring, and Mirroring
Authors: Fox Raymond
Published: November 2020

The critical role of the teacher is laying the paradigmatic groundwork for students’ learning to be professional. Teachers manifest in their comportment the intellectual, affective, and ethical bases of professional expertise. Their very conduct, enhanced by knowledge, embodies the essential message about how to be a helper. Three interwoven processes—modeling, mentoring, and mirroring—form the basis for professional education. They are converging and commingling processes, not independent elements in learning, as described here for intelligibility’s sake; they are multidirectional in influence and spiral back on each other, comprising a wholesome and fulfilling professional educational venture. Each individual mode is important in and of itself, but their interrelationship is the compelling element. Modeling is a complex process involving observation, imitation, and identification by students of the teacher. It occurs whether or not you intend it or not. Many of the same skills and conditions that promote client growth promote student growth. Strive to create an ambiance that engages students. Seek to engross them at a level that allows them to take the concepts they learn, as well as the examples you provide, whether tacitly or explicitly, from seeing you practice with them in class, and transfer them to their contact with clients. The words you utter, the actions you take, the manner in which you conduct the class are carefully observed and considered by students. They attend to your preparation, enthusiasm, and relatedness as lived lessons about how to deliver these same attributes and functions with clients. They observe your unspoken feedback—how your tone and facial expression reveal whether you are attuned and on the right track. In your interaction with students, whether consciously or not, you continually display your own competence in your discipline. Students observe how you practice what you preach in your dealings with them, with colleagues, with syllabus material, nascent ideas, and theories. They inevitably appraise your ability to facilitate communication, manage dilemmas, encourage mutuality, and foster cooperation in working associations with others. They assess your patience, availability, and skill.
Effort Appears Inadequate in the Modern World:Our Identities Are Shaped by Our Real- Life Chances
Authors: Elliott Willliam , Lewis Melinda
Published: November 2020

In its simplest form, the American dream is the belief that success should be determined by effort, not unfair advantage. This idea is embedded in the psyche of most Americans and shapes the way we collectively view individuals’ outcomes. It forms the lens through which we judge social policies that undergird opportunities or compound disadvantage. It is powerful enough to influence the way that people see their own success and failure and that of others. It can blind Americans to the structural forces that chart our fates. Indeed, Americans who want so badly to believe that there is a logic to the forces that shape their outcomes and a real path to their promised future may even excuse patently unfair institutions and the injustices they perpetuate. While these system- justifying beliefs can buffer people from the stress of contemplating abject inequity, as evidence mounts that things are not working as they should, defenses slip, doubts rise, and cracks emerge in the American dream. Today, there is a growing sense that this dream is more nostalgic memory than an accurate representation of the way the world works. A 2014 survey found that 48% of Americans believed that the American dream once was true but is not true anymore. These doubts represent more than just whispered anxieties or casual statements of political frustration. Instead, we contend that belief in the American dream is an expression of deeply rooted faith in our institutions and their ability to deliver on their promises, which in turn becomes a covenant in modern governance. This means that Americans’ increasing skepticism about whether institutions will ensure that their efforts pay off threatens the foundation of civil society. In other words, our inclination to rationalize societal arrangements has limits. When we can no longer explain away inequitable outcomes from schools, the labor market, and government policies, the social contract Americans have forged together is broken.
Toward an Equitable Opportunity Pipeline:The Creation of a Uniquely American Proposal for the 21st Century
Authors: Elliott Willliam , Lewis Melinda
Published: November 2020

The promising effects of relatively small-dollar Children’s Savings Accounts (CSAs) have catalyzed tremendous energy for universal provision of early asset accounts. Within the CSA field and among many close observers, there is consensus that CSA policy should start with an account for every child in the United States. As described in chapter 4, however, the promise of small- dollar CSAs is a bit of a double-edged sword. For some, the policy objective has become the account itself. Some proponents of this view believe that Children’s Savings Accounts are like infrastructure, a sort of social utility that has to be put in place—like plumbing—so that the benefits that these structures confer can then “flow.” Others may be eager for what seems like an easier win and consoled by the prospect of getting “something”—like the college-saver identities that early assets can cultivate—for nearly “nothing.” However, because this policy conceptualization fails to fully account for the problem of wealth inequality and its devastating effects on equitable educational attainment and upward mobility, such CSAs will likely fall short of the potentially transformative impact of children’s asset ownership. In this chapter, we discuss our understanding of CSA policy evolution in order to present a case for how CSAs can go beyond mere “plumbing” to truly revolutionize higher education finance. In accordance with Kingdon’s theory of how agendas advance, we then outline a policy suited to the problem to which our political system must respond: fractures in the opportunity pipeline that derail children’s futures and threaten the American dream. Instead of starting with what might be the easiest immediate win, we frame a vision of the powerful institutional tool children need: Opportunity Investment Accounts (OIAs), an essential investment in an American opportunity pipeline. Our emphasis on OIAs as conduits for meaningful wealth transfer rather than empty pipes does not mean that there are no benefits to small-dollar children’s savings. As described in chapter 5, a growing body of evidence attests to the intrinsic value of dedicated educational assets, early in a child’s life, even when small in amount.
Introduction:The Mediation of Failed Mediation
Authors: Pinchevski Amit
Published: November 2020

In 1995 Binjamin Wilkomirski published a book that was to become a source of fierce controversy. Fragments: Memories of a Wartime Childhood recounts Wilkomirski’s experiences of surviving alone two concentration camps as a small Jewish child from Poland. Having lived most of his life as Bruno Dössekker, the adopted son of a Swiss couple, Wilkomirski claimed to have discovered his true identity through a long psychoanalytic process, which led to writing his story. The book quickly received popular and critical acclaim and won a number of literary prizes, including the National Jewish Book Award. What happened next is fairly well known: a 1998 newspaper article cast doubt as to the authenticity of Wilkomirski’s account, revealing instead the story of a Bruno Grosjean, the illegitimate son of an unmarried woman who had given him away for adoption in Switzerland. The book’s publisher then commissioned a historian to look into the allegations, which were consequently found to be correct. The book previously described as “achingly beautiful” and “morally important” was now declared as fake and its author a fraud. The Wilkomirski case has since figured in debates on Holocaust memory as a cautionary tale about the facility with which one can pass as a survivor— and convince a worldwide audience. The book was discontinued as memoir only later to be released in tandem with the historical study finding it false. While Wilkomirski’s memories may have been fabricated, the way they were depicted in the book is a fairly accurate description of traumatic memory. Even if the content of these memories is made- up their structure very much conforms to a psychology textbook entry on post- trauma. Evidently Wilkomirski was aware of this fact, as in the afterword to the book, he urges others in a similar situation to “cry out their own traumatic childhood memories.”
Videography and Testimony
Authors: Pinchevski Amit
Published: November 2020

Modern technological media and psychoanalysis are historically coextensive, so argues Friedrich Kittler. During the last decades of the nineteenth century, a profound transformation had taken place in the material conditions of communication—what Kittler terms Aufschreibesystem (literally “writing-down system,” translated as “discourse network”). Prior to that transformation, writing, in its various manifestations, was the dominant medium of information storage and transmission. When writing was the prevailing writing-down system, all forms of data had to pass through the “bottleneck of the signifier.” With the technological transformation that followed, the symbolic mediation of writing was supplemented by the non-symbolic writing-down system of sight and sound: the audio channel of the phonograph and the visual channel of the cinematograph. As opposed to writing, these media are unselective inscription devices, capturing the intentional together with the unintentional, data and noise, indiscriminately as they come. It is against this background that psychoanalysis appears as a contemporaneous method of recording both intentional and unintentional expressions: the meanings conveyed by speech together with the halts, parapraxes, and stutters—which are rendered at least as meaningful as the intended meanings. Psychoanalysis has a technological counterpart in the form of late nineteenth-century media: the psychic and the technical constitute two parallel mechanisms for the inscription of traces, with the logic of the latter partially informing the former. Sigmund Freud has an unlikely partner in Thomas Edison: the talking cure and the discovery of the unconscious are concomitant with phonography and the mechanization of nonsense. Yet media and psychoanalysis, argues Kittler, do not only supplement the medium of writing; they also take on various tasks of cultural mediation previously under the monopoly of script. One such task is the writing of the past, historiography understood most literally, which, following Kittler’s reasoning, is also transformed by modern media to include the aural and the visual. That the past is experienced through its media traces was obvious enough to any citizen of the twentieth century.
Oxidation– Reduction Reactions
Authors: Sposito Garrison
Published: November 2020

Soils become flooded occasionally by intense rainfall or by runoff, and a significant portion of soils globally underlies highly productive wetlands ecosystems that are inundated intermittently or permanently. Peat-producing wetlands (bogs and fens) account for about half the inundated soils, with swamps and rice fields each accounting for about one-sixth. Wetlands soils hold about one-third of the total nonfossil fuel organic C stored below the land surface, which is about the same amount of C as found in the atmosphere or in the terrestrial biosphere. This C storage is all the more impressive given that wetlands cover less than 6% of the global land area. On the other hand, wetlands ecosystems are also significant locales for greenhouse gas production. They constitute the largest single source of CH4 entering the atmosphere, emitting about one-third the global total, with half this amount plus more than half the global N2O emissions coming from just three rice-producing countries. A soil inundated by water cannot exchange O2 readily with the atmosphere. Therefore, consumption of O2 and the accumulation of CO2 ensue as a result of soil respiration. If sufficient humus metabolized readily by the soil microbiome (“labile humus”) is available, O2 disappearance after inundation is followed by a characteristic sequence of additional chemical transformations. This sequence is illustrated in Fig. 6.1 for two agricultural soils: a German Inceptisol under cereal cultivation and a Philippines Vertisol under paddy rice cultivation. In the German soil, which was always well aerated prior to its sudden inundation, NO3- is observed to disappear from the soil solution, after which soluble Mn(II) and Fe(II) begin to appear, whereas soluble SO42- is depleted (left side of Fig. 6.1). The appearance of the two soluble metals results from the dissolution of oxyhydroxide minerals (Section 2.4). Despite no previous history of inundation, CH4 accumulation in the soil occurs and increases rapidly after SO42- becomes undetectable and soluble Mn(II) and Fe(II) levels have become stabilized. During the incubation time of about 40 days, the pH value in the soil solution increased from 6.3 to 7.5, whereas acetic acid (Section 3.1) as well as H2 gas were produced.
Soil Adsorption Phenomena
Authors: Sposito Garrison
Published: November 2020

Adsorption experiments involving soil particles typically are performed in a sequence of three steps: (1) reactio of an adsorptive (ion or molecule) with a soil contacting an aqueous solution of known composition under controlled temperature and applied pressure for a prescribed period of time, (2) separationof the wet soil slurry from the supernatant aqueous solution, and (3) quantitationof the ion or molecule of interest, both in the aqueous solution and in the separated soil slurry along with its entrained soil solution. The reaction step can be performed in either a closed system (batch reactor) or an open system (flow-through reactor), and it can proceed over a time period that is either relatively short (to investigate adsorption kinetics) or very long (to investigate adsorption equilibration). The separation step is similarly open to choice, with centrifugation, filtration, or gravitational settling being conventional methods to achieve separation. The quantitation step, in principle, should be designed not only to determine the moles of adsorbate and unreacted adsorptive, but also to verify whether unwanted side reactions, such as precipitation of the adsorptive or dissolution of the adsorbent, have influenced the experiment. After reaction between an adsorptive i and a soil adsorbent, the moles of i adsorbed per kilogram of dry soil is calculated with the standard equation ni ≡ niT − Mwmi where niT is the total moles of species i per kilogram dry soil in a slurry (batch process) or a soil column (flow-through process), Mw is the gravimetric water content of the slurry or soil column (measured in kilograms water per kilogram dry soil), and mi is the molality (moles per kilogram water) of species i in the supernatant solution (batch process) or effluent solution (flow-through process). Equation 8.1 defines the surface exces, ni, of an ion or molecule adsorptive that has become an adsorbate. Formally, ni is the excess number of moles of i per kilogram soil relative to its molality in the supernatant solution. As mentioned in Section 7.2, this surface excess may be a positive, zero, or negative quantity.
Soil Acidity
Authors: Sposito Garrison
Published: November 2020

A soil is acidic if the pH value of the soil solution is less than 7.0. This condition is met in many soils where rainfall exceeds evapotranspiration, including Alfisols, Histosols, Inceptisols, Oxisols, Spodosols, and Ultisols—almost half of the ice-free land area worldwide. Soils of the humid tropics offer examples of acidic soils (Ultisols and Oxisols), as do soils of forested regions in the temperate zones of Earth (Alfisols, Histosols, Inceptisols, and Spodosols). Soils in peat-producing wetlands and those influenced strongly by oxidation reactions, such as rice-producing uplands, can be mentioned as examples in which the biota play a direct role in acidification. The phenomena that produce a given proton concentration in the soil solution to render it acidic are complex and interrelated. Those pertaining to sources and sinks for protons are shown in Fig. 11.1, which is a special case of Fig. 1.4 with “free cation or anion” in the center of the latter figure now interpreted as H+. In addition to the biogeochemical determinants of soil acidity, the field-scale transport processes wetfall (rain, snow, throughfall), dryfall (deposited solid particles), and interflow (lateral movement of soil water beneath the land surface down hill slopes) carry protons into a soil solution from external sources. Their existence and that of proton-exporting processes, such as volatilization and erosion, underscore the fact that the soil solution is an open natural water system subject to anthropogenic inputs that may dominate the development of soil acidity. Industrial effluents, such as sulfur and nitrogen oxide gases or mining waste waters, that produce acidic deposition or infiltration, and nitrog-enous fertilizers, the transformation and transport of which produce acidic soil conditions, are examples of anthropogenic inputs. Despite all this complexity, proton cycling in acidic soils at field scales has been quantified well enough to allow some general conclusions to be drawn. Acidic deposition, production of CO2(g) and humus, plus proton biocycling, all serve to increase soil solution acidity, whereas proton adsorption and mineral weathering serve to decrease it.
E. O. Wilson: The Biophilic Sublime
Authors: Gross Alan G.
Published: November 2020

Sitting in the same rain forest where Darwin penned these words more than a century earlier, E. O. Wilson shares the identical “cathedral feeling,” the identical sense of the biological sublime evoked by the diversity of the biosphere: “Hold[ing] still for long intervals to study a few centimeters of tree trunk or ground, [and] finding some new organism at each shift in focus.” It is a feeling for his fellow creatures exhibited in every aspect of E. O. Wilson’s life: his efforts to understand ant society, his discovery of sociobiology as means of understanding all societies, and, finally, his efforts to preserve the diversity of the biosphere in which all societies must find their place. For Wilson, environmental ethics flows naturally from the cathedral feeling he shares with Darwin, their sense of the biological sublime. It is 1969 and there is a knock on Wilson’s office door. It signals the arrival a talented German entomologist, Bert Hölldobler, invited to Harvard for an extended stay. The two hit it off almost immediately; eventually, Hölldobler returns to Harvard as a full professor. While his command of English improves, his German accent never entirely disappears, an accent, Wilson feels, that lends weight to his lectures: his is the authentic voice of German science. Friends and collaborators, the two produce a stream of science that culminates in the publication of The Ants. The award of the Pulitzer for this book is Wilson’s opportunity simultaneously to signal and make light of his achievements. The book “weighed 7.5 pounds, fulfilling my criterion of a magnum opus—a book when dropped from a three-story building is big enough to kill a man.” The award is also an opportunity to express his gratitude to the institution that continued to nurture his talent. At the monthly college meeting, he recalls, “I stood and basked in the applause of the Harvard faculty. Bless my soul, the Harvard faculty. Where could I go from here but down.” By this time, however, his co-author has left Harvard. The daily drudgery of turning out grant proposals has taken its toll.
Organic Functional Group Interconversion
Authors: Taber Douglass F.
Published: November 2020

Gojko Lalic of the University of Washington developed (Angew. Chem. Int. Ed. 2014, 53, 6473) conditions for the preparation of the fluoride 2 by SN2 displacement of the triflate 1. Ross M. Denton of the University of Nottingham showed (Tetrahedron Lett. 2014, 55, 799) that a polymer-bound phosphine oxide activated with oxalyl bromide would convert an alcohol 3 to the bromide 4. The polymer could be filtered off and reactivated directly. Jonas C. Peters and Gregory C. Fu of Caltech devised (J. Am. Chem. Soc. 2014, 136, 2162) a photochemically-activated Cu catalyst that mediated the displacement of the bromide 5 by the amide 6 to give 7. Mark L. Trudell of the University of New Orleans used (Synthesis 2014, 46, 230) an Ir catalyst to couple the amide 9 with the alcohol 8, leading to 10. Tohru Fukuyama of Nagoya University converted (Org. Lett. 2014, 16, 727) the unsaturated aldehyde 11 into the ester 12. As the transformation proceeded via proton­ation of the enolized acyl cyanide, the less stable diastereomer was formed kinetically. Brindaban C. Ranu of the Indian Association for the Cultivation of Science developed (Org. Lett. 2014, 16, 1040) conditions for the coupling of an alkenyl halide 13 with a phenol, leading to the vinyl ether 14. Inter alia, this would be a convenient way to hydrolyze an alkenyl halide to the aldehyde. Vinyl ethers can also be oxidized directly to the ester, and to the unsaturated aldehyde. Pallavi Sharma and John E. Moses of the University of Lincoln observed (Org. Lett. 2014, 16, 2158) that the cyanation of the alkenyl halide 15 delivered 16, with retention of the geometry of the alkene. Jitendra K. Bera of the Indian Institute of Technology Kanpur uncovered (Tetrahedron Lett. 2014, 55, 1444) “on water” conditions for the hydrolysis of a terminal alkyne 17 to the methyl ketone 18. Jiannan Xiang and Weimin He of Hunan University prepared (Eur. J. Org. Chem. 2014, 2668) the keto phosphonate 20 by hydrolysis of the alkynyl phosphonate 19. Ken-ichi Fujita of the National Institute of Advanced Industrial Science and Technology cyclized (Tetrahedron Lett. 2014, 55, 3013) the alkyne 21 with CO₂, leading to 22.
Functional Group Oxidation and Reduction
Authors: Taber Douglass F.
Published: November 2020

Christophe Darcel and Jean- Baptiste Sortais of the CNRS-Université Rennes 1 reduced (Chem. Commun. 2013, 49, 10010) an acid 1 to the aldehyde 2 with a Mn catalyst under photostimulation. The same authors also used (Angew. Chem. Int. Ed. 2013, 52, 8045) an Fe catalyst to reduce an ester (not illustrated) to the corresponding aldehyde. Yasushi Tsuji of Kyoto University employed (Adv. Synth. Catal. 2013, 355, 3420) a Pd catalyst to reduce acid to the aldehydes. Chao-Jun Li of McGill University found (Angew. Chem. Int. Ed. 2013, 52, 11871) that a Ag catalyst in water would reduce an aldehyde 3 to the alcohol 4. Ketones were not reduced under these conditions. David Milstein of the Weizmann Institute of Science devised (Angew. Chem. Int. Ed. 2013, 52, 14131) an Fe catalyst for the E-selective reduction of an alkyne 5 to the alkene 6. Debabrata Maiti of IIT Bombay effected (Chem. Commun. 2013, 49, 8362) reductive cleavage of a nitrile 7 to the alkane 8. Aryl nitriles were also reduced. Professor Li used (Eur. J. Org. Chem. 2013, 6496) an Ir catalyst and hydrazine under H-transfer conditions to reduce an alcohol 9 to the hydrocarbon 10. Kenneth M. Nicholas of the University of Oklahoma reduced (Chem. Commun. 2013, 49, 8199) the diol 11 to the alkene 12 with a V catalyst. Qiang Liu of Lanzhou University and Li- Zhu Wu of the Technical Institute of Physics and Chemistry showed (Eur. J. Org. Chem. 2013, 7528) that irradiation in the presence of a photoredox catalyst and a Hantzsch ester removed the sulfonyl group of 13. Selective oxidation is a powerful tool for organic synthesis. Eike B. Bauer of the University of Missouri St. Louis oxidized (Chem. Commun. 2013, 49, 5889) the diol 15 to the ketone 16 with an Fe catalyst and 30% hydrogen peroxide. Yan- qin Yuan of Lishui University and Jiannan Xiang of Hunan University selectively (Org. Lett. 2013, 15, 4654) thiolated the ether 17 to 18, that has the aldehyde oxidation state. Chengjian Zhu of Nanjing University converted (Adv. Synth. Catal. 2013, 355, 3558) the aldehyde 19 to the thioester 20 by oxidation in the presence of diphenyl disulfide.
New Methods for Reduction and for Oxidation
Authors: Taber Douglass F.
Published: November 2020

Clemens Krempner of Texas Tech University devised (Chem. Eur. J. 2014, 20, 14959) a very active Al catalyst for the Meerwein-Ponndorf-Verley reduction of a ketone 1 to the alcohol 2. Louis Fensterbank and Cyril Ollivier of UMPC and Jean-Philippe Goddard of the Université de Haute-Alsace showed (Adv. Synth. Catal. 2014, 356, 2756) that visible light could mediate the reduction of the O-thiocarbamate 3 to 4. Soon Hyeok Hong of Seoul National University used (Org. Lett. 2014, 16, 4404) hydrogen from the diol 6 to reduce the nitrile 5, leading directly to the protected amine 7. Alex Adronov of McMaster University (J. Org. Chem. 2014, 79, 7728) and Thibault Cantat of Gif- sur-Yvette (Chem. Commun. 2014, 50, 9349) observed that an aryl amide 8 could be reduced to the amine 9 under conditions that left alkyl amides unchanged. Paul J. Chirik of Princeton University developed (J. Am. Chem. Soc. 2014, 136, 13178) a Co catalyst for the alcohol- directed reduction of a proximal alkene, converting 10 selectively to 11. Yoichiro Kuninobu and Motomu Kanai of the University of Tokyo used (Synlett 2014, 25, 1869) stoichiometric Mo(CO)₆ to desulfurize 12 to 13. Utpal Bora of Tezpur University oxidized (Tetrahedron Lett. 2014, 55, 5029) the alcohol 14 to the aldehyde 15 with t-butyl hydroperoxide, using the inexpensive and reusable VOSO₄ as the catalyst. The oxidation of an alcohol to the acid is often car­ried out in two steps, alcohol to aldehyde and aldehyde to carboxylic acid. Kenneth B. Wagener of the University of Florida developed (Tetrahedron Lett. 2014, 55, 4452) a protocol for the direct oxidation of an alcohol 16 to the acid 17. Prodeep Phukan of Gauhati University devised (Tetrahedron Lett. 2014, 55, 5358) a catalyst-free procedure for the oxidation of a primary alcohol 18 to the ester 19. The aldehyde cor­responding to 18 (not illustrated) was also efficiently oxidized to 19. Katsuhiko Moriyama and Hideo Togo of Chiba University effected (Org. Lett. 2014, 16, 3812) the oxidative debenzylation of 20 to the ketone 21.
Functional Group Protection: The Pohl Synthesis of β-1,4-Mannuronate Oligomers
Authors: Taber Douglass F.
Published: November 2020

D. Srinivasa Reddy of the National Chemical Laboratory converted (Org. Lett. 2015, 17, 2090) the selenide 1 to the alkene 2 under ozonolysis conditions. Takamitsu Hosoya of the Tokyo Medical and Dental University found (Chem. Commun. 2015, 51, 8745) that even highly strained alkynes such as 4 can be generated from a sulfinyl vinyl triflate 3. An alkyne can be protected as the dicobalt hexacarbonyl complex. Joe B. Gilroy and Mark S. Workentin of the University of Western Ontario found (Chem. Commun. 2015, 51, 6647) that following click chemistry on a non-protected distal alkyne, deprotection of 5 to 6 could be effected by exposure to TMNO. Stefan Bräse of the Karlsruhe Institute of Technology and Irina A. Balova of Saint Petersburg State University showed (J. Org. Chem. 2015, 80, 5546) that the bend of the Co complex of 7 enabled ring-closing metathesis, leading after deprotection to 8. Morten Meldal of the University of Copenhagen devised (Eur. J. Org. Chem. 2015, 1433) 9, the base-labile protected form of the aldehyde 10. Nicholas Gathergood of Dublin City University and Stephen J. Connon of the University of Dublin developed (Eur. J. Org. Chem. 2015, 188) an imidazolium catalyst for the exchange deprotection of 11 to 13, with the inexpensive aldehyde 12 as the acceptor. Peter J. Lindsay-Scott of Eli Lilly demonstrated (Org. Lett. 2015, 17, 476) that on exposure to KF, the isoxa­zole 14 unraveled to the nitrile 15. Masato Kitamura of Nagoya University observed (Tetrahedron 2015, 71, 6559) that the allyl ester of 16 could be removed to give 17, with the other alkene not affected. Benzyl ethers are among the most common of alcohol protecting groups. Yongxiang Liu and Maosheng Cheng of Shenyang Pharmaceutical University showed (Adv. Synth. Catal. 2015, 357, 1029) that 18 could be converted to 19 simply by expo­sure to benzyl alcohol in the presence of a gold catalyst. Reko Leino of Åbo Akademi University developed (Synthesis 2015, 47, 1749) an iron catalyst for the reductive benzylation of 20 to 21. Related results (not illustrated) were reported (Org. Lett. 2015, 17, 1778) by Chae S. Yi of Marquette University.
C–H Functionalization: The Shaw Synthesis of E-δ-Viniferin
Authors: Taber Douglass F.
Published: November 2020

Thomas Lectka of Johns Hopkins University reported (J. Org. Chem. 2014, 79, 8895) a simple protocol for free radical monofluorination, exemplified by the conversion of 1 to 2. Michael K. Hilinski of the University of Virginia used (Org. Lett. 2014, 16, 6504) a catalytic amount of the ketone 4 to mediate the oxidation of 3 to 5. Oxidation of 3 with DMDO gave the regioisomeric tertiary alcohol (not illustrated). Jeung Gon Kim and Sukbok Chang of KAIST used (Chem. Commun. 2014, 50, 12073) an Ir catalyst to convert 6 selectively to the primary sulfonamide 7. Paul J. Chirik of Princeton University employed (J. Am. Chem. Soc. 2014, 136, 12108) a Co catalyst to effect the migration of the internal alkene of 8 to the terminal alkene, that then underwent dehydrogenative silylation with 9 to deliver the allyl silane 10. Jiang Cheng of Changzhou University developed (J. Org. Chem. 2014, 79, 9847) conditions for the aminoalkylation of cyclohexane 11 with 12 to give 13. Ilhyong Ryu of Osaka Prefecture University and Maurizio Fagnoni of the University of Pavia observed (Chem. Sci. 2014, 5, 2893) high selectivity in the addition of 14 to 15. Of the five possible regioisomers, 16 dominated. In another light-mediated transformation, Shin Kamijo of Yamaguchi University and Masayuki Inoue of the University of Tokyo added (Chem. Sci. 2014, 5, 4339) 17 to 18 to give 19. Huw M. L. Davies of Emory University established (J. Am. Chem. Soc. 2014, 136, 17718) conditions for the enantioselective alkylation of a methyl ether 21 with 20 to give the ester 22. Selective methyl insertion was observed even with much more complex substrates. The trichloroethyl ester was critical for this transformation. James A. Bull of Imperial College London effected (Org. Lett. 2014, 16, 4956) selec­tive cis-arylation of the proline-derived amide 23 with 24 to give 25. E. Peter Kündig of the University of Geneva coupled (Chem. Eur. J. 2014, 20, 15021) the amine 27 with 26, then cyclized that product to the indoline 28. The enantiomeric Pd cata­lyst delivered the regioisomeric C–H insertion product.
Alkenes
Authors: Griffith Allison K. , Lambert Tristan H.
Published: November 2020

The α-C–H functionalization of piperidine catalyzed by tantalum complex 1 to pro­duce amine 2 was developed (Org. Lett. 2013, 15, 2182) by Laurel L. Schafer at the University of British Columbia. An asymmetric diamination of diene 3 with diaziri­dine reagent 4 under palladium catalysis to furnish cyclic sulfamide 5 was developed (Org. Lett. 2013, 15, 796) by Yian Shi at Colorado State University. Enantioenriched β-fluoropiperdine 8 was prepared (Angew. Chem. Int. Ed. 2013, 52, 2469) via amino­fluorocyclization of 6 with hypervalent iodide 7, as reported by Cristina Nevado at the University of Zurich. Erick M. Carreira at ETH Zürich disclosed (J. Am. Chem. Soc. 2013, 135, 6814) a ruthenium-catalyzed hydrocarbamoylation of allylic formamide 9 to yield pyrrolidone 10. Hans-Günther Schmalz at the University of Köln disclosed (Angew. Chem. Int. Ed. 2013, 52, 1576) an asymmetric hydrocyanation of styrene 11 with Ni(cod)₂ and phosphine–phosphite ligand 12 to yield exclusively the branched cyanide 13. A simi­lar transformation of styrene 11 to the hydroxycarbonylated product 15 was catalyzed (Chem. Commun. 2013, 49, 3306) by palladium complex 14, as reported by Matthew L. Clarke at the University of St Andrews. Feng-Ling Qing at the Chinese Academy of Sciences found (Angew. Chem. Int. Ed. 2013, 52, 2198) that the hydrotrifluoromethylation of unactivated alkene 16 to 17 was catalyzed by silver nitrate. The same transformation was also reported (J. Am.Chem. Soc. 2013, 135, 2505) by Véronique Gouverneur at the University of Oxford using a ruthenium photocatalyst and the Umemoto reagent 18. Clark R. Landis at the University of Wisconsin, Madison reported (Angew. Chem. Int. Ed. 2013, 52, 1564) a one-pot asymmetric hydroformylation using 21 followed by Wittig olefination to transform alkene 19 into the γ-chiral α,β-unsaturated carbonyl compound 20. Debabrata Mati at the Indian Institute of Technology Bombay found (J. Am. Chem. Soc. 2013, 135, 3355) that alkene 22 could be nitrated stereoselectively with silver nitrite and TEMPO to form alkene 23. Damian W. Young at the Broad Institute disclosed (Org. Lett. 2013, 15, 1218) that a macrocyclic vinylsiloxane 24, which was synthesized via an E-selective ring clos­ing metathesis reaction, could be functionalized to make either E- or Z-alkenes, 25 and 26.
Arrays of Stereogenic Centers: The Shin/Chandrasekhar Synthesis of (+)-Lactacystin
Authors: Taber Douglass F.
Published: November 2020

Kami L. Hull of the University of Illinois established (J. Am. Chem. Soc. 2014, 136, 11256) conditions for the diastereoselective hydroamination of 1 with 2 to give 3. Jon C. Antilla of the University of South Florida employed (Org. Lett. 2014, 16, 5548) an enantiomerically-pure Li phosphate to direct the opening of the prochiral epoxide 4 to 5. Jordi Bujons and Pere Clapés of IQAC-CSIC engineered (Chem. Eur. J. 2014, 20, 12572) an enzyme that mediated the enantioselective addition of glycolaldehyde 7 to an aldehyde 6, leading to 8. Takahiro Nishimura of Kyoto University set (J. Am. Chem. Soc. 2014, 136, 9284) the two stereogenic centers of 11 by adding 10 to the diene 9. Amir H. Hoveyda of Boston College added (J. Am. Chem. Soc. 2014, 136, 11304) the propargylic anion derived from 13 to the aldehyde 12 to give, after oxida­tion, the diol 14. Yujiro Hayashi of Tohoku University constructed (Adv. Synth. Catal. 2014, 356, 3106) 17 by the combination of 15 with 16. Yitzhak Apeloig and Ilan Marek of Technion-Israel Institute of Technology prepared (J. Org. Chem. 2014, 79, 12122) the bromo diol 20 by rearranging the adduct between the alkyne 19 and the acyl silane 18. James P. Morken, also of Boston College, effected (J. Am. Chem. Soc. 2014, 136, 17918) enantioselective coupling of 22 with the bis-borane 21. The prod­uct allyl borane added to benzaldehyde to give the alcohol 23. Sentaro Okamoto of Kanagawa University reduced (Org. Lett. 2014, 16, 6278) the aryl oxetane 24 to an intermediate that coupled with allyl bromide to give the alco­hol 25. In the presence of catalytic CuCN, the alternative diastereomer was the major product. Erick M. Carreira of ETH Zürich used (Angew. Chem. Int. Ed. 2014, 53, 13898) a combination of an Ir catalyst and an organocatalyst to couple the aldehyde 27 with the allylic alcohol 26. The four possible combinations of enantiomerically pure catalysts worked equally well, enabling the preparation of each of the four enan­tiomerically pure diastereomers of 28.
C–O Ring-Containing Natural Products: Cyanolide A (Krische), Bisabosqual A (Parker), Iso-Eriobrucinol A (Hsung), Trichodermatide A (Hiroya), Batrachotoxin Core (Du Bois)
Authors: Lambert Tristan H.
Published: November 2020

Michael J. Krische at the University of Texas at Austin developed (Angew. Chem. Int. Ed. 2013, 52, 4470) a total synthesis of cyanolide A 7 in only seven steps, a sequence so short it is shown here in its entirety. Diol 1 was subjected to enantioselective cat­alytic bisallylation under iridium catalysis to furnish 2 with very high levels of ste­reocontrol. Cross metathesis using ruthenium catalyst 3 first with ethyl vinyl ketone and then with ethylene resulted in the production of pyran 4. Glycosylation of 4 with phenylthioglycoside 5, stereoselective reduction of the ketone function, and oxidative cleavage of the olefin then furnished the carboxylic acid 6. Finally, dimerization of 6 with 2-methyl-6-nitrobenzoic anhydride (MBNA) yielded cyanolide A. Kathlyn A. Parker at Stony Brook University reported (J. Am. Chem. Soc. 2013, 135, 582) a tandem radical cyclization strategy for the total synthesis of bisabosqual A 11. The key substrate 9 was prepared in three steps from the diester 8. Treatment of 9 with tri-s-butylborane and TTMS in the presence of air induced the tandem 5-exo, 6-exo radical cyclization to produce the complete core 10 of the natural product as a mixture of diastereomers, which could be equilibrated. Some further redox maneu­vers then led to bisabosqual A. Richard P. Hsung at the University of Wisconsin, Madison disclosed (Org. Lett. 2013, 15, 3130) a very brief synthesis of iso-eriobrucinol A and related isomers using a unique cascade sequence. First, phloroglucinol 12 and citral 13 were condensed using piperidine and acetic anhydride. The product of this operation was the tetracy­clic cyclobutane 14, the result of an oxa-[3+3] annulation followed by a stepwise, cat­ionic [2+2] cycloaddition. Treatment of 14 with methyl propiolate in the presence of catalytic indium(III) chloride under microwave irradiation furnished iso-eriobrucinol A, as well as the isomeric natural product iso-eriobrucinol B. A concise approach to trichodermatide A 19 was developed (Angew. Chem. Int. Ed. 2013, 52, 3546) by Kou Hiroya at Musashino University. Aldehyde 16, which was syn­thesized from L-tartaric acid, was condensed with 1,3-cyclohexanedione in the presence of piperidine, resulting in diketone 17.
C–N Ring Construction: The Glorius Synthesis of ent-Monomorine
Authors: Taber Douglass F.
Published: November 2020

Ryan Gilmour of the Westfälische Wilhelms-Universität Münster employed (Chem. Eur. J. 2014, 20, 794) an organocatalyst to direct the enantioselective aziridination of 1 to 2. Vanessa Kar-Yan Lo and Chi-Ming Che of Hong Kong University devised (Angew. Chem. Int. Ed. 2014, 53, 2982) a Ru catalyst for the enantioselective aziridi­nation (not illustrated) of terminal alkenes. Shu-Li You of the Shanghai Institute of Organic Chemistry and Aiwen Lei of Wuhan University described (Angew. Chem. Int. Ed. 2014, 53, 2443) the Pd-mediated carbonylation of 3 to the β-lactam 4. Professor You reported (J. Am. Chem. Soc. 2014, 136, 6590) the enantioselective allylation of a pyrrole 5 with 6 to give the imine 7. Maria-Paz Cabal and Carlos Valdés of the University of Oviedo showed (Eur. J. Org. Chem. 2014, 1672) that the cycliza­tion of 8 to 9 proceeded with predictable high diastereocontrol. In one pot, Darren J. Dixon of the University of Oxford combined (ACS Catal. 2014, 4, 634) 10 and 11 to give 12 in high ee. The addition of 13 to 14 to give 15 described (Nature Chem. 2014, 6, 47) by Takashi Ooi of Nagoya University set two adjacent quaternary centers with control of both relative and absolute configuration. Scott E. Denmark of the University of Illinois devised (J. Am. Chem. Soc. 2014, 136, 8915) a catalyst for the enantioselective electrophilic cyclization of 16 to 17 with control of sidechain stereochemistry. Using commercial acetone cyanohydrin 19, Christian V. Stevens of Ghent University cyclized (Eur. J. Org. Chem. 2014, 1296) 18 to the nitrile 20. George W. J. Fleet, also of the University of Oxford, used (Eur. J. Org. Chem. 2014, 2053) similar conditions to convert the sugar-derived acetonide 21 into 22. Michael B. Tropak of the University of Toronto and Dilip P. Dhavale of the University of Pune showed (J. Org. Chem. 2014, 79, 4398) that the nitrone derived from 21 added to an alkene 23 with high facial selectivity, leading to the piperidine 24. In the course of a synthesis of syringolin A, Satoshi Ichikawa of Hokkaido University effected (Angew. Chem. Int. Ed. 2014, 53, 4836) intramolecular Ugi three-component coupling of the isonitrile 25, the acid 26, and the amine 27, leading to the macrolactam 28.
Substituted Benzenes: The Li Synthesis of Rubriflordilactone A
Authors: Taber Douglass F.
Published: November 2020

Cheol-Hong Cheon of Korea University (J. Org. Chem. 2014, 79, 7277) and Toshiyuki Kamei and Toyoshi Shimada of the Nara National College of Technology (Tetrahedron Lett. 2014, 55, 4245) described the ring bromination of arene boronates. The boronate can then be removed, enabling the conversion of 1 to 2. Yu Rao of Tsinghua University constructed (Chem. Commun. 2014, 50, 15037) the sulfone 5 by coupling the arenes 3 and 4 with K2S2O8. Igor Larrosa of Queen Mary University of London assembled (Chem. Sci. 2014, 5, 3509) the biphenyl 8 by arylating 6 with the iodide 7. Guy Bertrand of the University of California, San Diego showed (J. Am. Chem. Soc. 2014, 136, 13594) that under Au catalysis, the aniline 9 was sufficiently nucleophilic to add in a conjugate sense to the enone 10 to give 11. Hideo Togo of Chiba University optimized (Eur. J. Org. Chem. 2014, 6077) condi­tions for the selective ortho formylation of a phenol 12. The crude reaction mixture could also be directly oxidized with I2/ NH3 to give the nitrile 13. Silas P. Cook of Indiana University ortho metalated (J. Am. Chem. Soc. 2014, 136, 13130; Angew. Chem. Int. Ed. 2014, 53, 11065) the benzamide 14, then used an iron catalyst to couple that intermediate with a halide 15, leading to the alkylated product 16. As with the phenol 12 and the benzamide 14, aromatic functionalization has usu­ally been directed by a functional group directly attached to the ring. Daqin Shi and Yingsheng Zhao of Soochow University showed (Chem. Sci. 2014, 5, 4962) that a longer tether can be effective, as illustrated by the conversion of 17 to 19. Debabrata Maiti of the Indian Institute of Technology Bombay also used (Org. Lett. 2014, 16, 5760) a longer tether for the selective meta functionalization of 20 to 22. Motohiro Sonoda of Osaka Prefecture University constructed (Tetrahedron Lett. 2014, 55, 5302) the phenol 25 by acid-mediated rearrangement of the Diels–Alder adduct of 24 with the furan 23. Anthony G. M. Barrett of Imperial College London devised (J. Org. Chem. 2014, 79, 8706) conditions for the iodinative cyclization of 26 to 27.