bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemists Who Work in Industry
Authors: Brown Jeannette E.
Published: November 2020

Dr. Dorothy J. Phillips (Fig. 2.1) is a retired industrial chemist and a member of the Board of Directors of the ACS. Dorothy Jean Wingfield was born in Nashville, Tennessee on July 27, 1945, the third of eight children, five girls and three boys. She was the second girl and is very close to her older sister. Dorothy grew up in a multi- generational home as both her grandmothers often lived with them. Her father, Reverend Robert Cam Wingfield Sr., born in 1905, was a porter at the Greyhound Bus station and went to school in the evenings after he was called to the ministry. He was very active in his church as the superintendent of the Sunday school; he became a pastor after receiving an associate’s degree in theology and pastoral studies from the American Baptist Theological Seminary. Her mother, Rebecca Cooper Wingfield, occasionally did domestic work. On these occasions, Dorothy’s maternal grandmother would take care of the children. Dorothy’s mother was also very active in civic and school activities, attending the local meetings and conferences of the segregated Parent Teachers Association (PTA) called the Negro Parent Teachers Association or Colored PTA. For that reason, she was frequently at the schools to talk with her children’s teachers. She also worked on a social issue with the city to move people out of the dilapidated slum housing near the Capitol. The town built government subsidized housing to relocate people from homes which did not have indoor toilets and electricity. She was also active in her Baptist church as a Mother, or Deaconess, counseling young women, especially about her role as the minister’s wife. When Dorothy went to school in 1951, Nashville schools were segregated and African American children went to the schools in their neighborhoods. But Dorothy’s elementary, junior high, and high schools were segregated even though the family lived in a predominately white neighborhood. This was because around 1956, and after Rosa Park’s bus boycott in Montgomery, AL, her father, like other ministers, became more active in civil rights and one of his actions was to move to a predominately white neighborhood.
Chemists Who Work for the National Labs or Other Federal Agencies
Authors: Brown Jeannette E.
Published: November 2020

Dr. Patricia Carter Sluby (Fig. 5.1) is a primary patent examiner retired from the US Patent and Trademark Office and formerly a registered patent agent. She is also the author of three books about African American inventors and their patented inventions. Patricia’s father is William A. Carter Jr., and her mother is Thelma LaRoche Carter. Her father was the first black licensed master plumber in Richmond, VA, and his father also had the same distinction in Columbus, OH, years earlier. Her father was born in Philadelphia, PA, and attended college. Her grandfather went from Virginia to look for work in Canada and became a stonemason. Later he relocated back to the United States, where he soon married in Boston, MA, and several of his children were born there. Later, the family moved to Philadelphia where Patricia’s father was born. Her mother, who attended Hampton Institute, taught school and later managed the office for Patricia’s father’s business. Patricia’s mother was born and raised in Richmond, as were most of her maternal relatives. Patricia had three brothers. They were all born during segregation in Richmond, the former capital of the Confederacy. Patricia was born on February 15, in Richmond. She attended kindergarten through eighth grade in segregated schools that were within walking distance of home. In school, they studied from hand-me-down books, but her black teachers were well trained and well informed. They had bachelor’s degrees; some had master’s or even PhD degrees. To go to high school, Patricia took a city bus across to the east side of town, to the newly built school for black students, which incorporated eighth grade through twelfth grade. Her teachers were excellent instructors who lived in her neighborhood and knew her parents quite well. The teachers looked out for the neighborhood kids and acted as surrogate parents out­side the confines of the home. Teachers and principals were also great mentors, dedicated to their craft; they encouraged students to understand the world and function as responsible adults. Patricia excelled in science and math.
Virtual Testimony and the Digital Future of Traumatic Past
Authors: Pinchevski Amit
Published: November 2020

At the base of all Holocaust testimony projects lies a common commitment: to record and preserve the stories of those who survived the catastrophe as told in their own voices. When it comes to survivors’ testimonies, the messenger is as important as the message. The first to subscribe to this reasoning was the American psychologist David Boder, who in 1946 set out to interview survivors in refugee camps across Western Europe. Equipped with what was then the state- of- the- art technology—an Armour Model 50 wire recorder—Boder went on to produce what was the first audio testimony of the Holocaust. The wire recorder, developed in the 1940s by Marvin Camras, Boder’s colleague at the Illinois Institute of Technology, for the U.S. military, was a portable and remarkably durable device that utilized thin steel wires rolled into spools to produce an electromagnetic recording (see Fig. 4.1 below). As Boder later commented, the device “offered a unique and exact means of recording the experiences of displaced persons. Through the wire recorder the displaced person could relate in his own language and in his own voice the story of his concentration camp life.” Studying wire- recorded narratives led him to devise a “traumatic index” by means of which “each narrative may be assessed as to the category and number of experiences bound to have a traumatizing effect upon the victim.” Boder’s 1949 monograph, I Did Not Interview the Dead, invites readers to find indications of trauma implicit in selected transcripts of recorded narratives. The premise seems to be that, to the extent that such traumatic impact exists, it should be discoverable textually. Yet the same technology that made Boder’s project ingenious was also the reason for its relative obscurity. Wire recording was soon to give way to tape recording, consequently condemning Boder’s wire spools to obsolescence and the testimonies they held to near oblivion. The short- lived medium precluded access to the recorded material.
Soil Humus
Authors: Sposito Garrison
Published: November 2020

Biomoleculesare compounds synthesized to sustain the life cycles of organisms. In soil humus, they are usually products of litter degradation, root excretion, and microbial metabolism, ranging in molecular structure from simple organic acids to complex biopolymers. Organic acids are among the best-characterized biomolecules. Table 3.1 lists five aliphatic (meaning the C atoms are arranged in open-chain structures) organic acids associated commonly with the soil microbiome. These acids contain the unit R—COOH, where COOH is the carboxyl groupand R represents either H or an organic moiety. The carboxyl group can lose its proton easily within the normal range of soil pH (see the third column of Table 3.1) and so is an example of a Brønsted acid. The released proton, in turn, can attack soil minerals to induce their decomposition (see Eq. 1.2), whereas the carboxylate anion (COO-) can form soluble complexes with metal cations, such as Al3+, that are released by mineral weathering [for example, in Eq. 1.7, rewrite oxalate, C2O42-, as (COO-) 2]. The total concentration of organic acids in the soil solution ranges up to 5 mM. These acids tend to have very short lifetimes because of biocycling, but they abide as a component of soil humus, especially its water-soluble fraction, because they are produced continually by microorganisms and plant roots. Formic acid (methanoic acid), the first entry in Table 3.1, is a monocarboxylic acid produced by bacteria and found in the root exudates of maize. Acetic acid (ethanoic acid) also is produced microbially—especially under anaerobic conditions—and is found in root exudates of grasses and herbs. Formic and acetic acid concentrations in the soil solution range from 2 to 5 mM. Oxalic acid (ethanedioic acid), which is ubiquitous in soils, and tartaric acid (D- 2,3-dihydroxybutanedioic acid) are dicarboxylic acids produced by fungi and excreted by plant roots; their soil solution concentrations range from 0.05 to 1 mM. The tricarboxylic citric acid (2-hydroxypropane- 1,2,3-tricarboxylic acid) is also produced by fungi and excreted by plant roots. Its soil solution concentration is less than 0.05 mM.
The Soil Solution
Authors: Sposito Garrison
Published: November 2020

The soil solution was introduced in Section 1.2 as a liquid water repository for dissolved solutes. Speaking more precisely, one can define the soil solution as the aqueous liquid phase in soil having a composition influenced by exchanges of matter and energy with soil air, soil minerals, and the soil biota. This more precise concept identifies the soil solution as an open system, and its designation as a phase means two things: (1) that it has uniform macroscopic properties (for example, temperature and composition) and (2) that it can be isolated from the soil profile and investigated experimentally in the laboratory. Uniformity of macroscopic properties obviously cannot be attributed to the entire aqueous phase in a soil profile, but instead is associated with a sufficiently small element of volume in the profile still large enough to include many pores. As is the case for soil humus (Section 3.2), the problem of isolating a sample of the soil solution without artifacts is an ongoing challenge to soil chemistry, but several techniques for removing the aqueous phase from soil into the laboratory have been established as operational compromises between chemical accuracy and analytical convenience. Among these techniques, the most widely applied in situ methods are drainage water collection and vacuum extraction, whereas the common ex situ methods include displacement by another fluid and extraction by vacuum, applied pressure, or centrifugation. The in situ techniques are influenced by whatever disturbance to a soil profile and, therefore, natural aggregate structure and water flow patterns, has occurred because of apparatus installation. They yield a sample of the soil solution from a largely undefined profile volume and they differ in whether they provide the flux compositionor the resident compositionof a soil solution. A flux composition, which is relevant to chemical weathering and, more broadly, to solute transport in soils, is measured in a soil solution sample obtained by natural flow into a collector, as occurs in a pan lysimeter (Fig. 4.1).
Reduction of Organic Functional Groups
Authors: Taber Douglass F.
Published: November 2020

Cornelis J. Elsevier of the University of Amsterdam developed (ACS Catal. 2014, 4, 1349) an improved Pd-based protocol for the hydrogenation of an alkyne 1 to the Z-alkene 2. Yongbo Zhou and Shuang-Feng Yin of Hunan University showed (Adv. Synth. Catal. 2014, 356, 765) that under Cu catalysis, hypophosphorous acid selec­tively reduced the terminal alkyne of 3 to the ene-yne 4. Hidefumi Makabe of Shinshu University found (Tetrahedron Lett. 2014, 55, 2822) that the iodoalkyne 5 was reduced to the iodoalkene 6 by diimide, conveniently generated from the arenesulfo­nyl hydrazide. Manat Pohmakotr of Mahidol University used (Eur. J. Org. Chem. 2014, 1708) P- 2 Ni to reduce the sulfoxide 7 to the alkene 8. Shinya Furakawa and Takayuki Komatsu of the Tokyo Institute of Technology devised (ACS Catal. 2014, 4, 1441) a Pd catalyst for the selective reduction of the nitro group of 9 to the aniline 10. Hiroshi Kominami of Kinki University employed (Chem. Commun. 2014, 50, 4558) a Ti- promoted Ag catalyst to deoxygenate the epoxide 11 to the alkene 12. Benjamin R. Buckley and K. G. Upul Wijayantha of Loughborough University described (Synlett 2014, 25, 197) an alternative protocol (not illustrated) for epoxide deoxygenation. Xiaohui Fan of Lanzhou Jiaotong University observed (Eur. J. Org. Chem. 2014, 498) that the reduction of 13 to 14 proceeded without cyclopropane opening, sug­gesting the reaction did not involve substantial charge separation. Michel R. Gagné of the University of North Carolina deployed (Angew. Chem. Int. Ed. 2014, 53, 1646) cat­alytic trispentafluorophenylborane to selectively reduce 15 to 16. Gojko Lalic of the University of Washington reduced (Angew. Chem. Int. Ed. 2014, 53, 752) a secondary iodide 17 to the hydrocarbon 18 under Cu catalysis. Primary bromides and triflates could also be reduced, while many other functional groups, including tosylates, were stable. Marc Lemaire of the Université Claude-Bernard Lyon 1 converted (Tetrahedron Lett. 2014, 55, 23) the nitrile 19 to the aldehyde 20 by V-catalyzed reduction followed by hydrolysis. Matthias Beller of the Universität Rostock showed (Chem. Eur. J. 2014, 20, 4227) that a nitrile 21 could be reduced to the amine 22 with very little by- product dimer.
Developments in Flow Chemistry
Authors: Taber Douglass F.
Published: November 2020

Klavs S. Jensen of MIT showed (Angew. Chem. Int. Ed. 2014, 53, 470) that “batch” kinetics could be developed in flow by online IR analysis and continuous control. Professor Jensen also demonstrated (Org. Process Res. Dev. 2014, 18, 402) the contin­uous flow production of an active pharmaceutical product, the direct renin inhibitor aliskiren, over two steps and two crystallizations, starting from two advanced interme­diates. Michael Werner and Rainer E. Martin of Hoffmann-La Roche AG Basel com­bined (Angew. Chem. Int. Ed. 2014, 53, 1704) flow synthesis with a flow-based bioassay to develop structure–activity relationships for a series of β-secretase inhibitors. Carlos Mateos of Lilly S. A. and C. Oliver Kappe of the University of Graz used (J. Org. Chem. 2014, 79, 223) flow photolysis to promote the bromination of 1 to 2. Alessandro Palmieri of the University of Camerino and Stefano Protti of the University of Pavia added (Adv. Synth. Catal. 2014, 356, 753) the aldehyde 3 to the acceptor 4 to give, after in-flow reduction, the lactone 5. Peter H. Seeberger of the Max Planck Institute Mühlenberg showed (Org. Lett. 2014, 16, 1794) that the tum­bling action of flow photolysis made the production of 7 by the unlinking of 6 from the polymer bead particularly efficient. Enzymes can also be used under flow conditions. Jörg Pietruszka of the Heinrich-Heine-Universität Düsseldorf employed (Adv. Synth. Catal. 2014, 356, 1007) com­mercial laccase to prepare 10 by coupling 8 with 9. Gas–liquid mixing under flow conditions can also be effective. Núria López of ICIQ Catalonia and Javier Pérez-Ramírez of ETH Zurich developed (Chem. Eur J. 2014, 20, 5926) conditions for the selective hydrogenation of an alkyne 11 to the cis alkene 12. Jun-ichi Yoshida of Kyoto University trapped (Chem. Eur J. 2014, 20, 7931) the inter­mediate organolithium from 13 with CO₂ to give a carboxylate that was carried on to the purifiable O-Su ester 14, ready for further coupling. Timothy F. Jamison, also of MIT, prepared (Angew. Chem. Int. Ed. 2014, 53, 3353) the amino phenol 17 by add­ing the chloromagnesium amide from 16 to the intermediate benzyne from 15, then oxidizing the product with air.
Reactions of Alkenes: The Usami Synthesis of (−)-Pericosine E
Authors: Taber Douglass F.
Published: November 2020

Dasheng Leow of the National Tsing Hua University used (Eur. J. Org. Chem. 2014, 7347) photolysis to activate the air oxidation of hydrazine to generate diimide, that then reduced 1 selectively to 2. Kevin M. Peese of Bristol-Myers Squibb effected (Org. Lett. 2014, 16, 4444) ring-closing metathesis of 3 followed by in situ reduction to form 4. Jitendra K. Bera of the Indian Institute of Technology Kanpur effected (J. Am. Chem. Soc. 2014, 136, 13987) gentle oxidative cleavage of cyclooctene 5 to the dialde­hyde 6. Arumugam Sudalai of the National Chemical Laboratory observed (Org. Lett. 2014, 16, 5674) high regioselectivity in the oxidation of the alkene 7 to the ketone 8. Hao Xu of Georgia State University also observed (J. Am. Chem. Soc. 2014, 136, 13186) high regioselectivity in the oxidation of the alkene 9 with 10, leading to the urethane 11. Justin Du Bois of Stanford University developed (J. Am. Chem. Soc. 2014, 136, 13506) mild conditions for the net double amination of the alkene 12 with 13, leading to 14. Jiaxi Xu and Pingfan Li of the Beijing University of Chemical Technology devised (Org. Lett. 2014, 16, 6036) a protocol for the allylic thiomethylation of an alkene with 16, converting 15 to 17. Matthias Beller of the Leibniz-Institüt für Katalyse combined (Chem. Eur. J. 2014, 20, 15692) hydroformylation, aldol condensation, and reduction to convert the alkene 18 to the ketone 19. Phil S. Baran of Scripps/La Jolla added (Angew. Chem. Int. Ed. 2014, 53, 14382) the diazo dienone 21 to the alkene 20 to give, after exposure to HCl, the arylated product 22. Markus R. Heinrich of the Friedrich-Alexander-Universität Erlangen-Nürnberg employed (Chem. Eur. J. 2014, 20, 15344) Selectfluor as both an oxidizing and a fluorinating agent in the related addition of 24 to 23 to give 25. Debabrata Maiti at the Indian Institute of Technology Bombay activated (J. Am. Chem. Soc. 2014, 136, 13602) the ortho position of 27, then added that interme­diate to 26 to give 28.
Construction of Alkylated Stereogenic Centers: The Zhu Synthesis of (−)-Rhazinilam
Authors: Taber Douglass F.
Published: November 2020

Zheng Huang of the Shanghai Institute of Organic Chemistry (J. Am. Chem. Soc. 2014, 136, 15501) and Zhan Lu of Zhejiang University (Org. Lett. 2014, 16, 6452) effected enantioselective hydroboration of α-alkyl styrenes, as illustrated by the conversion of 1 to 2. Stephen L. Buchwald of MIT devised (J. Am. Chem. Soc. 2014, 136, 15913) a Cu catalyst for the anti-Markovnikov hydroamination of 3 with 4 to give 5. John F. Hartwig of the University of California, Berkeley developed (Angew. Chem. Int. Ed. 2014, 53, 8691, 12172) an Ir catalyst for the enantioselective coupling of 6 with 7 to give 8.
C–O Ring Formation
Authors: Lambert Tristan H.
Published: November 2020

The enantioselective bromocyclization of dicarbonyl 1 to form dihydrofuran 3 using thiocarbamate catalyst 2 was developed (Angew. Chem. Int. Ed. 2013, 52, 8597) by Ying-Yeung Yeung at the National University of Singapore. Access to dihydrofuran 5 from the cyclic boronic acid 4 and salicylaldehyde via a morpholine-mediated Petasis borono-Mannich reaction was reported (Org. Lett. 2013, 15, 5944) by Xian-Jin Yang at East China University of Science and Technology and Jun Yang at the Shanghai Institute of Organic Chemistry. Chiral phosphoric acid 7 was shown (Angew. Chem. Int. Ed. 2013, 52, 13593) by Jianwei Sun at the Hong Kong University of Science and Technology to catalyze the enantioselective acetalization of diol 6 to form tetrahydrofuran 8 with high stereoselectivity. Jan Deska at the University of Cologne reported (Org. Lett. 2013, 15, 5998) the conversion of glutarate ether 9 to enantiopure tetrahy­drofuranone 10 by way of an enzymatic desymmetrization/oxonium ylide rearrange­ment sequence. Perali Ramu Sridhar at the University of Hyderabad demonstrated (Org. Lett. 2013, 15, 4474) the ring-contraction of spirocyclopropane tetrahydropyran 11 to produce tetrahydrofuran 12. Michael A. Kerr at the University of Western Ontario reported (Org. Lett. 2013, 15, 4838) that cyclopropane hemimalonate 13 underwent conver­sion to vinylbutanolide 14 in the presence of LiCl and Me₃N•HCl under microwave irradiation. Eric M. Ferreira at Colorado State University developed (J. Am. Chem. Soc. 2013, 135, 17266) the platinum-catalyzed bisheterocyclization of alkyne diol 15 to fur­nish the bisheterocycle 16. Chiral sulfur ylides such as 17, which can be synthesized easily and cheaply, were shown (J. Am. Chem. Soc. 2013, 135, 11951) by Eoghan M. McGarrigle at the University of Bristol and University College Dublin and Varinder K. Aggarwal at the University of Bristol to stereoselectively epoxidize a variety of alde­hydes, as exemplified by 18. The amine 20-catalyzed tandem heteroconjugate addition/Michael reaction of quinol 19 and cinnamaldehyde to produce bicycle 21 with very high ee was reported (Chem. Sci. 2013, 4, 2828) by Jeffrey S. Johnson at the University of North Carolina, Chapel Hill. Quinol ether 22 underwent facile photorearrangement–cycloaddition to 23 under irradiation, as reported (J. Am. Chem. Soc. 2013, 135, 17978) by John A. Porco, Jr. at Boston University and Corey R. J. Stephenson, now at the University of Michigan.
C–N Ring Construction: The Waser Synthesis of Jerantinine E
Authors: Taber Douglass F.
Published: November 2020

James A. Bull of Imperial College London prepared (J. Org. Chem. 2013, 78, 6632) the aziridine 2 with high diastereocontrol by adding the anion of diiodomethane to the imine 1. Karl Anker Jørgensen of Aarhus University observed (Chem. Commun. 2013, 49, 6382) high ee in the distal aziridination of 3 to give 4. Benito Alcaide of the Universidad Complutense de Madrid and Pedro Almendros of ICOQ- CSIC Madrid reduced (Adv. Synth. Catal. 2013, 355, 2089) the β-lactam 5 to the azetidine 6. Hiroaki Sasai of Osaka University added (Org. Lett. 2013, 15, 4142) the allenoate 8 to the imine 7, delivering the azetidine 9 in high ee. Tamio Hayashi of Kyoto University, the National University of Singapore, and A*STAR devised (J. Am. Chem. Soc. 2013, 135, 10990) a Pd catalyst for the enanti­oselective addition of the areneboronic acid 11 to the pyrroline 10 to give 12. Ryan A. Brawn of Pfizer (Org. Lett. 2013, 15, 3424) reported related results. Nicolai Cramer of the Ecole Polytechnique Fédérale de Lausanne developed (J. Am. Chem. Soc. 2013, 135, 11772) a Ni catalyst for the cyclization of the formamide 13 to the lactam 14. Andrew D. Smith of the University of St. Andrews used (Org. Lett. 2013, 15, 3472) an organocatalyst to cyclize 15 to 16. Jose L. Vicario of the Universidad del Pais Vasco effected (Synthesis 2013, 45, 2669) the multicomponent coupling of 17, 18, and 19, mediated by an organocatalyst, to construct 20 in high ee. André Beauchemin of the University of Ottawa explored (J. Org. Chem. 2013, 78, 12735) the thermal cyclization of ω-alkenyl hydroxyl amines such as 21. Abigail G. Doyle of Princeton University developed (Angew. Chem. Int. Ed. 2013, 52, 9153) a Ni catalyst for the enantioselective addition of aryl zinc bromides such as 24 to the pro­chiral 23, to give 25 in high ee. Dennis G. Hall of the University of Alberta developed (Angew. Chem. Int. Ed. 2013, 52, 8069) an in situ preparation of the allyl boronate 26 in high ee. Addition to the aldehyde 27 proceeded with high diasteroselectivity.
C–N Ring Construction: The Hattori Synthesis of (+)-Spectaline
Authors: Taber Douglass F.
Published: November 2020

Magnus Rueping of RWTH Aachen University found (Chem. Commun. 2015, 51, 2111) that under Fe catalysis, a Grignard reagent would couple with the iodoazetidine 1 to give the substituted azetidine 2. Timothy F. Jamison of MIT established (Chem. Eur. J. 2015, 21, 7379) a protocol for converting 3, readily available from commercial homoserine lactone, to the alkylated azetidine 4. Long-Wu Ye of Xiamen University used (Chem. Commun. 2015, 51, 2126) a gold catalyst to cyclize 5, readily prepared in high ee, to the versatile ene sulfonamide 6. Chang- Hua Ding and Xue-Long Hou of the Shanghai Institute of Organic Chemistry added (Angew. Chem. Int. Ed. 2015, 54, 1604) the racemic aziridine 7 to the enone 8 to give the pyrrolidine 9 in high ee. Arumugam Sudalai of the National Chemical Laboratory employed (J. Org. Chem. 2015, 80, 2024) proline as an organocatalyst to mediate the addition of 11 to 10, leading to the pyrrolidine 12. Aaron D. Sadow of Iowa State University developed (J. Am. Chem. Soc. 2015, 137, 425) a Zr catalyst for the enantioselective cyclization of the prochiral 13 to 14. Masahiro Murakami of Kyoto University devised (Angew. Chem. Int. Ed. 2015, 54, 7418) a Rh catalyst for the enantioselective ring expansion of the photocycliza­tion product of 15 to the enamine 16. Sebastian Stecko and Bartlomiej Furman of the Polish Academy of Sciences reduced (J. Org. Chem. 2015, 80, 3621) the carbohydrate-derived lactam 17 with the Schwartz reagent to give an intermediate that could be coupled with an isonitrile, leading to the amide 18. Lei Liu of Shandong University oxidized (Angew. Chem. Int. Ed. 2015, 54, 6012) the alkene 19 in the presence of 20 to give 21. Tomislav Rovis of Colorado State University optimized (J. Am. Chem. Soc. 2015, 137, 4445) a Zn catalyst for the addition of 22 to the nitro alkene 23, leading, after reduction, to the piperidine 24. Carlos del Pozo and Santos Fustero of the Universidad de Valencia used (Org. Lett. 2015, 17, 960) a chiral auxiliary to direct the cyclization of 25 to the bicyclic amine 26. In another illustration of the use of microwave irradiation to activate amide bond rotation, G. Maayan of Technion showed (Org. Lett. 2015, 17, 2110) that 27 could be cyclized efficiently to the medium ring lactam 28.
Preparation of Substituted Benzenes: The Beaudry Synthesis of Arundamine
Authors: Taber Douglass F.
Published: November 2020

Stephen G. DiMagno of the University of Nebraska developed (Chem. Eur. J. 2015, 21, 6394) a protocol for the clean monoiodination of 1 to 2. The bromomethylation (or chloromethylation, with HCl) of a benzene derivative is straightforward with formal­dehyde and HBr. Naofumi Tsukada of Shizuoka University designed (Organometallics 2015, 34, 1191) a Cu catalyst that mediated the coupling of an alkyne with the benzyl bromide so produced, effecting net propargylation of 3 with 4 to give 5. Triazenes such as 7, versatile intermediates for organic synthesis, are usually prepared by diazotization of the corresponding aniline. Kay Severin of the Ecole Polytechnique Fédérale de Lausanne established (Angew. Chem. Int. Ed. 2015, 54, 302) an alternative route from the aryl Grignard reagent 6. Ping Lu and Yanguang Wang of Zhejiang University showed (Chem. Commun. 2015, 51, 2840) that dimethylformamide could serve as the carbon source for the conversion of 8 to the nitrile 9. Junha Jeon of the University of Texas at Arlington effected (J. Org. Chem. 2015, 80, 4661; Chem. Commun. 2015, 51, 3778) the reductive ortho silylation of 10 to give 11. Vladimir Gevorgyan of the University of Illinois at Chicago found (Angew. Chem. Int. Ed. 2015, 54, 2255) that the phenol derivative 12 could be ortho carboxylated, leading to 13. Lutz Ackermann of the Georg-August-Universität Göttingen, starting (Chem. Eur. J. 2015, 21, 8812) with the designed amide 14, effected ortho metala­tion followed by coupling, to give the methylated product 15. Tetsuya Satoh and Masahiro Miura of Osaka University used (Org. Lett. 2015, 17, 704) the dithiane of 16 to direct ortho metalation. Coupling with acrylate followed by reductive desulfu­rization led to the ester 17. Jin-Quan Yu of Scripps/La Jolla designed (Angew. Chem. Int. Ed. 2015, 54, 888) the phenylacetamide 18 to direct selective meta metalation, leading to the unsat­urated aldehyde 19. In an extension of the Catellani protocol, Guangbin Dong of the University of Texas prepared (J. Am. Chem. Soc. 2015, 137, 5887) the biphenyl 21 by net meta metalation of the benzylamine 20. Several methods for the de novo assembly of benzene derivatives have recently been put forward. Rajeev S. Menon of the Indian Institute of Chemical Technology condensed (Org. Lett. 2015, 17, 1449) the unsaturated aldehyde 22 with the sulfonyl ester 23 to give 24.
Organocatalyzed C–C Ring Construction: The Jørgenson Synthesis of (+)-Estrone
Authors: Taber Douglass F.
Published: November 2020

Ana Maria Faísca Phillips and Maria Teresa Barros of the Universidade Nova de Lisboa added (Eur. J. Org. Chem. 2014, 152) the bromo ester 1 to cinnamaldehyde 2 to give the cyclopropyl phosphonate 3 in high ee. Mukund P. Sibi and Jayaraman Sivaguru of North Dakota State University used (Angew. Chem. Int. Ed. 2014, 53, 5604) an organocatalyst to mediate the 2+2 photocycloaddition of 4, leading to 5. Shu-Li You of the Shanghai Institute of Organic Chemistry expanded (Org. Lett. 2014, 16, 1810) the four-membered ring of 6 to create the cyclopentanone 7 in high ee. Damien Bonne and Jean Rodriguez of Aix-Marseille Université condensed (Chem. Eur. J. 2014, 20, 410) the cyclopentanone 8 with 9 to give 10. Santanu Mukherjee of the Indian Institute of Science, Bangalore added (Chem. Sci. 2014, 5, 1627) the lac­tone 12 to the prochiral 11 to give 13 with remarkable diastereo- and enantiocontrol. Yixin Lu of the National University of Singapore constructed (Angew. Chem. Int. Ed. 2014, 53, 5643) the cyclopentene 16 by adding 14 to the allene 15. Efraim Reyes and Jose L. Vicario of the Universidad del País Vasco prepared (Chem. Eur. J. 2014, 20, 2145) the highly substituted cyclohexene 19 by combining 17 and 18. Maurizio Benaglia of the Università degli Studi di Milano added (Adv. Synth Catal. 2014, 356, 493) the ketone 20 to 21 to create the cyclohexanone 22. Ben W. Greatrex of the University of New England in Australia used (J. Org. Chem. 2014, 79, 5088) an organocatalyst to cyclize the symmetrical dialdehyde 23 to the α-hydroxy ketone 24. Dieter Enders of RWTH Aachen added (Org. Lett. 2014, 16, 2954) the β-keto ester 25 to 26 to give an intermediate that was further condensed with 27 to complete the preparation of 28. Eric N. Jacobsen of Harvard University prepared (Angew. Chem. Int. Ed. 2014, 53, 5912) the cycloheptenone 30 by the enantioselective intermolecular addition of the pyrylium salt derived from 29 to ethyl vinyl ether. Bor-Cherng Hong of the National Chung Cheng University initiated (Org. Lett. 2014, 16, 2724) the assembly of the steroid derivative 33 by the enantioselective addition of 32 to the unsaturated aldehyde 31.
The Snyder Synthesis of Psylloborine A
Authors: Taber Douglass F.
Published: November 2020

In addition to the monomeric coccinellid alkaloids produced by the ladybug, some dimeric alkaloids, exemplified by psylloborine A 3, have been isolated. Scott A. Snyder of Scripps/Florida initially attempted a direct dimerization strategy for the assembly of 3, but when that failed, he devised (J. Am. Chem. Soc. 2014, 136, 9743) a route to the tethered dimer 1, that could indeed be cyclized to 2, the immediate precursor to 3. The starting material for both 9, the lower half of 1, and 13, the upper half of 1, was the commercial, enantiomerically-pure piperidine 4. Metalation followed by allylation gave the desired trans diastereomer 5. Oxidative cleavage followed by con­densation with 6 gave the ester 7, that was hydrogenated, then converted with 8 to the desired phosphonate 9. To prepare 13, 4 was metalated and alkylated with methallyl bromide. The prod­uct 10 was carried on to the enone 12 by oxidative cleavage followed by the addition of 11, oxidative cleavage, and dehydration. Reduction to the desired diastereomer was achieved by conjugate addition of hydride in the presence of the sterically very demanding Yamamoto Lewis acid ATPH. Deprotection followed by oxidation then gave 13, that was condensed with 9 and deprotected to give 14. Selective deprotection followed by oxidation and condensation with 15 then led to 1. A key element in the design of this synthesis was the ability to easily tune the sul­fone activating group, to direct the proper order of bond formation. The vision was that regeneration of the enone and deprotection, with tetramethylguanidine, would lead to 16. The free amine would add to the saturated ketone to give an enamine, that would in turn add in a conjugate sense to the enone to give 17. Further deprotec­tion of 17 under acid conditions would again generate an enamine that, it was hoped, would, after further cyclization, add to the unsaturated sulfone to give 2. As illustrated, the 3,5-bis(trifluoromethyl)phenyl sulfone gave the best results. Desulfurization of 2 completed the synthesis of the complex dimeric alkaloid psylloborine A 3.
The Sato/Chida Synthesis of Paclitaxel (Taxol®)
Authors: Taber Douglass F.
Published: November 2020

Paclitaxel (Taxol®) 3 is widely used in the clinical treatment of a variety of cancers. Takaaki Sato and Noritaka Chida of Keio University envisioned (Org. Lett. 2015, 17, 2570, 2574) establishing the central eight-membered ring of 3 by the SmI2-mediated cyclization of 1 to 2. The starting point for the synthesis was the enantiomerically-pure enone 5, pre­pared from the carbohydrate precursor 4. Conjugate addition to 5 proceeded anti to the benzyloxy substituent to give, after trapping with formaldehyde and protection, the ketone 6. Reduction and protection followed by hydroboration led to 7, that was, after protection and deprotection, oxidized to 8. The second ring of 3 was added in the form of the alkenyl lithium derivative 9, prepared from the trisylhydrazone of the corresponding ketone. Hydroxyl-directed epoxidation of 10 proceeded with high facial selectivity, leading, after reduction and protection, to the cyclic carbonate 11. Allylic oxidation converted the alkene into the enone, while at the same time oxidizing the benzyl protecting group to the ben­zoate, to give 12. Reduction of the ketone 12 led to a mixture of diastereomers. In practice, only one of the diastereomers of 1 cyclized cleanly to 2, as illustrated, so the undesired diastereomer from the NaBH4 reduction was oxidized back to the enone for recycling. For convenience, only one of the diastereomers of 2 was carried forward. To establish the tetrasubstituted alkene of 3, the alkene of 2 was converted to the cis diol and on to the bis xanthate 13. Warming to 50°C led to the desired tet­rasubstituted alkene, sparing the oxygenation that is eventually required for 3. For convenience, to intercept 16, the intermediate in the Takahashi total synthesis, both xanthates were eliminated to give 14. Hydrogenation removed the disubsti­tuted alkene, and also deprotected the benzyl ether. Oxidation followed by Peterson alkene formation led to 15, that was carried on to the Takahashi intermediate 16 using the now-standard protocol for oxetane construction. It is a measure of the strength of the science of organic synthesis that Masahisa Nakada of Waseda University also reported (Chem. Eur. J. 2015, 21, 355) an elegant synthesis of 3 (not illustrated).
Prospects for Life on Other Planets
Authors: Deamer David W.
Published: November 2020

This book describes a hypothetical process in which populations of protocells can spontaneously assemble and begin to grow and proliferate by energy- dependent polymerization. This might seem to be just an academic question pursued by a few dozen researchers as a matter of curiosity, but in the past three decades advances in engineering have reached a point where both NASA and the European Space Agency (ESA) routinely send spacecraft to other planetary objects in our solar system. A major question being pursued is whether life has emerged elsewhere than on Earth. The limited funds available to support such missions require decisions to be made about target priorities that are guided by judgment calls. These in turn depend on plausible scenarios related to the origin of life on habitable planetary surfaces. We know that other planetary bodies in our solar system have had or do have conditions that would permit microbial life to exist and perhaps even to begin. By a remarkable coincidence, the two most promising objects for extraterrestrial life happen to represent the two alternative scenarios described in this book: An origin of life in conditions of hydrothermal vents or an origin in hydrothermal fields. This final chapter will explore how these alternative views can guide our judgment about where to send future space missions designed as life-detection missions. Questions to be addressed: What is meant by habitability? Which planetary bodies are plausible sites for the origin of life? How do the hypotheses described in this book relate to those sites? There is healthy public interest in how life begins and whether it exists elsewhere in our solar system or on the myriad exoplanets now known to orbit other stars. This has fueled a series of films, television programs, and science fiction novels. Most of these feature extrapolations to intelligent life but a few, such as The Andromeda Strain, explore what might happen if a pathogenic organism from space began to spread to the human population. There is a serious and sustained scientific effort—SETI, or Search for Extraterrestrial Intelligence—devoted to finding an answer to this question.
Winding Down
Authors: Rosenstein Donald L. , Yopp Justin M.
Published: November 2020

From the beginning the men had known, better than we did, that six sessions would not be enough. Changing the group to an open-ended format had been the right move, but we hadn’t resolved the question of when the group should end. The fathers were clearly piecing their lives back together and the reasons for continuing to meet were becoming less clear. As the group approached the three-year mark, attendance lagged. We wondered if it had run its course. One evening, we asked the men whether they wanted to keep meeting or if it was time to stop. We acknowledged that our work together had become increasingly collaborative but wanted them to know that they were not beholden to us. We never intended for the group to continue in perpetuity. Our focus had been to help them grieve and move forward. If they had reached that point, then they should to feel free to leave. The fathers seemed surprised when we raised this topic. They quickly dismissed the idea that they felt obligated to remain in the group. Uncharacteristically, Russ spoke first, “I’ve never felt pressured. I come because it helps.” The topic of discussion during that session was whether it was time to stop meeting. Each father knew that he would eventually leave but up until that moment Steve’s departure had been the only other occasion on which we discussed endings. Bruce reframed the issue: “Unless getting engaged and moving across state lines is the only ticket out the door, I guess we need to figure this out.” Karl approached the subject with his typical analytical style. “It sounds like there are two issues on the table. First, how does any one of us know when it’s time to stop coming? For Steve, it was easy: He got married and moved away. For the rest of us, the decision comes down to whether coming here is still helpful. Obviously, each of us has to answer that for ourselves. The second question is whether it’s time for the group as a whole to end.
Amateurs and Professionals in Chemistry: The Case of the Periodic System
Authors: Stewart Philip J.
Published: November 2020

Amateurs Have Made Valuable contributions to various sciences, including astronomy, geology, biology, and engineering. In chemistry they have been drawn to the periodic system of the elements, with its deceptive simplicity, its density of information, its aesthetic potential, and its implication of deep order in the universe. They have suggested novel ways of representing it visually, in particular spirals and lemniscates in two or three dimensions. However, in the course of a century and a half, professional chemists have generally ignored the amateur versions of the table, and contented themselves with a couple of utilitarian tabulations. Edward Mazurs, one of the two great historians of the periodic system, surveyed approximately 700 graphic representations produced between 1862 and 1972. He was obsessed with classification, and he counted 146 different types. It seems astonishing that out of all these only two have ever attained any lasting and widespread currency among professionals. Dmitri Mendeleev’s short form was rapidly taken up by chemists and remained the standard for half a century. It was compact and easy to read, and by the clever device of combining three or four groups of elements as column VIII it concealed the difference in length between what we now call the p block and the d block. Indeed it confused the two; Mendeleev’s predicted properties of scandium (in the d block) were based on those of boron (in the p block). His inability to deal with the f block did not attract attention because as yet so few lanthanoids were known and that the early actinoids behave rather like the first members of the d-block. In the interwar years, the standard medium-long form gradually displaced Mendeleev’s short form, and since the 1940s it has become ubiquitous. Mazurs classified it as his type IIC2-4, and he referenced it 67 times—more than any other type (pp. 175–180)—but he thought so poorly of it that he accorded less than a page to discussing it.
Unique Ethical Issues in Chemistry
Authors: Kovac Jeffrey
Published: November 2020

What makes chemistry unique? And how does this uniqueness reflect on chemistry’s unique concerns with ethics? As Roald Hoffmann (1995) argues, it is because chemistry is in the “tense middle,” occupying a space between several pairs of extremes. Perhaps most important, chemistry has always inhabited a frontier between science and technology, the pure and the applied, the theoretical and the practical (Bensaude-Vincent and Simon 2008). Unlike the other natural sciences, chemistry traces its origins both to philosophy and the craft tradition. Chemists are discoverers of knowledge and creators of new substances. The objects of study in chemistry, molecules and the macroscopic systems made up of molecules, are intermediate between the very small, the elementary particles, and the very large, the cosmos. Chemical systems are the right size to affect humans directly, for better or worse. They are the building blocks of biological organisms, they are the substances we eat and drink, they are the drugs that have improved human health dramatically over the past century, they comprise the materials we use to construct the products we use daily, but they are also the environmental pollutants that can plague our world. Chemicals can also be used as weapons. Being in the middle means that chemists face a unique set of ethical issues that I try to explicate in this chapter. These issues derive, in part, from the nature of chemistry as a science, a science that does not fit the neat picture drawn in the first chapter of textbooks. They also derive from the fact that ethics is an inquiry into right human conduct: What is a good life? Chemistry has perhaps contributed more to the betterment of human life than any other science, but at the same time has also contributed significantly to the deterioration of the environment. As explained in Chapter 3, much of chemistry is conducted in Pasteur’s quadrant, where both the search for fundamental knowledge and considerations of use are important. Chemical synthesis is perhaps the central activity of chemistry.
Fishing for Orcas
Authors: Colby Jason M.
Published: November 2020

Griffin had been receiving letters for weeks, and they painted a vivid picture of Namu’s impact on those who had seen the famous orca. “We are sorry that Namu is dead,” wrote seven-year-old Christopher. “I wish that you will get another whale.” A little girl declared, “I will mention in my prayer tonight for God to send Namu safely to Heaven and for God to watch over him always.” “We are so grateful we saw Namu only a few weeks ago,” wrote one local family. “He was so beautiful and gentle.” “Without our friend Namu, the water­front will be a lonely place,” added a mother in Seattle. “We hope you will consider getting another whale.” The notes helped, but Ted Griffin hadn’t been himself since his friend’s death. The process of forming the first close human bond with a killer whale had produced an intense emotional high, and the animal’s death sent him into a spiral of depression. Usually frenetic, the aquarium owner found himself list­less and untethered from reality. “At first I told myself he would come back, as I had believed my father would after he died,” he later wrote. “I had never faced the reality of death as a fact of life.” Try as he might, Griffin couldn’t pull himself together. “I wanted to shed my burden of guilt,” he reflected. “I had brought Namu into the polluted water where the bacteria had killed him. My loved one died tragically, and indirectly by my own hand.” As the weeks went by, his children became confused by their father’s behavior, and Joan grew worried. Friends suggested that he try bonding with another whale, but they might as well have urged him to replace a lost spouse or child. Something in Ted Griffin had died with Namu. Nearly fifty years later, he sat with me at his dining room table and tried to convey this change. “After Namu died, I kept trying to find that connection,” he explained. “I kept hoping for it with another animal, but I couldn’t find it.” So he turned his mind to business.
The Legend of Mike Bigg
Authors: Colby Jason M.
Published: November 2020

The crew wasn’t looking forward to this. It was the chilly morning of October 26, 1973, and a southeastern swell had been rolling into Pedder Bay for hours. But Sealand’s twenty-man team was more worried about the task of restraining Taku. The bull killer whale was enormous—at least twenty-two feet long—and although he seemed friendly, no one knew how he would react. Most of the men smoked nervously as they watched the black dorsal fin circle the pen. As the water calmed, Bill Cameron exited the galley of the Western Spray and lowered himself onto one of the logs bordering the pen. Bob Wright had hired the Pender Harbour fisherman to help handle the whales. Although a large man, Cameron had a gentle way about him. “You just have to treat them like herring,” he instructed. “You can’t spook them.” At his order, the men aboard three small skiffs slowly began to pull up the net. Taku didn’t like it. As his enclosure shrank, the orca squealed, slapping his pectoral fins on the water. In a nearby pen, another captured whale, Kandy, listened intently. “Dry him up!” yelled Cameron, and the crew pulled harder, drawing the mesh underneath the big orca. As his man-made pond vanished, Taku flopped onto his side, his upturned eye frantic with fear. To the relief of everyone, he didn’t lash out, and divers tilted him upright for an explosive breath. “I had a hunch he’d be that easy,” said Cameron. “It’s the females that are the tough ones.” But the hard part was yet to come. With the big whale secured, federal researcher Michael Bigg stepped away from a group of scientists gathered on deck. In his hands, he held a radio pack, which he had designed using Sealand’s captive orca Haida as a model. He planned to mount it on Taku in the first ever attempt to radio-tag a killer whale for release.