Professor Of Organic Chemistry Research Articles

NOBEL PRIZES: Corey wins for innovative syntheses

It is probable that no other chemist has developed such a comprehensive and varied assortment of methods which, often showing the simplicity of genius, have become commonplace in the synthesizing laboratory, said the Royal Swedish Academy of Sciences last week in awarding the 1990 Nobel Prize in Chemistry to organic chemistry professor Elias J. Corey of Harvard University. The academy also awarded the 1990 Nobel Prize Physics last week to Americans Jerome I. Friedman and Henry W. Kendall of Massachusetts Institute of Technology and Canadian Richard E. Taylor of Stanford University's Stanford Linear Accelerator Center. They won the prize for their pioneering investigations concerning deep inelastic scattering of electrons on protons and bound neutrons, which have been of essential importance the development of the quark model in particle physics. The work was carried out in the late 1960s and early 1970s. In awarding the chemistry prize, the academy cited Corey's development of theories ...

Systematic synthesis devised for oligosiloxanes

A strategy for syntheses of linear and branched oligosiloxanes of precisely defined structure has been devised by a team of chemists in the U.S. and Japan [J. Am. Chem. Soc, 112, 7077 (1990)]. Though most of the reactions are already known, this is the first time that chemists have combined them selectively to make rationally designed inorganic structures. The first demonstration of the synthetic strategy is syntheses of dendrimer (highly branched) molecules (C&EN, Feb. 22,1988, page 19). This shows that the method can serve to explore inorganic macromolecular architecture. On this side of the Pacific, participants were organic chemistry professor Satoru Masamune and postdoctoral fellow Takeshi Tsumuraya at Massachusetts Institute of Technology, supported by the National Science Foundation. Japanese collaborators were chemists Hiroaki Uchida, Yoshio Kabe, Koji Yoshino, and Akira Kawamata at household products maker Kao Corp., Tochigi. Kabe is now a faculty member at Tsukuba University, Ibaraki. The synthe...

Asymmetric synthesis takes big step forward

Chemists at the University of Illinois, Urbana-Champaign, have devised a cheap method for catalytic asymmetric epoxidation of unsubstituted olefins [ J. Am. Chem. Soc. , 112 , 2800 (1990)]. The technique may be applied to research syntheses of natural products and industrial production of drugs, pesticides, pheromones, and flavor and fragrance additives. Such widely applicable asymmetric syntheses take on a new importance in light of the regulations concerning marketing of enantiomeric versus racemic drugs expected this spring from the Food & Drug Administration. This achievement of organic chemistry professor Eric N. Jacobsen is the latest advance in efforts to make chiral compounds from olefins. It parallels the catalytic asymmetric epoxidation of allylic alcohols and catalytic asymmetric dihydroxylation of unsubstituted olefins devised by organic chemistry professor K. Barry Sharpless at Massachusetts Institute of Technology. Like the chemistry of Sharpless, the new reaction creates two dissymmetric ca...

Robert Sanderson Mulliken, 7 June 1896 - 31 October 1986

Robert Sanderson Mulliken was born on 7 June 1896 in Newburyport, Rhode Island. His father, Samuel Parsons Mulliken, was a Professor of Organic Chemistry at the Massachusetts Institute of Technology, to which he would travel a distance of some 30 miles every day on the Boston and Maine Railroad. Samuel’s income was modest, and the family had little contact with the more influential members of the community. “This may account”, says Robert in his autobiography (B 250)*, “for a deep-seated inferiority complex which I have had, especially toward people in authority, but not towards prominent scientists”. He recalls helping his father proofread his four-volume treatise A method for the identification of pure organic compounds '. “It is natural”, says Robert loyally, “that I became interested in science although I was strongly tempted to move in other directions, such as philosophy or other humanistic fields”. His mother Katherine W. Mulliken (a distant cousin of his father) formed a stronger bond with her son. She was a member of the Unitarian Church, and frequently took Robert along with her. She failed to persuade him to learn the piano, but succeeded in imbuing him with a sense of justice and of the beauty of nature. “I have sometimes experienced very strong feelings of intimacy with nature”, he writes (B 250) “but not of beauty in its laws”. His upbringing was strict and conventional and one gains the impression of an extremely well-behaved but rather shy child. He writes with lurking admiration about a red-haired classmate at the Jackman Grammar School, who became famous for his unconventional exploits and is quoted (B 250) as saying “my worst trouble is that I got my lessons done too quick”. Bossy Gillis, as he was called, rose rapidly in the community and was eventually elected mayor of Newburyport. Half a century later Robert Mulliken was invited back to Newburyport by another mayor, to have a street named after him.

Catenane synthesized in one step in 70% yield

Chemists at Sheffield University, England, have succeeded in making a [2]catenane in a one-step reaction in 70% yield. Catenanes are compounds whose cyclic components are intertwined like chain links. The number in brackets denotes the number of links. This accomplishment demonstrates what organic chemistry professor J. Fraser Stoddart calls structure-directed synthesis. Information is preprogramed into the reactants for efficient assembly of large molecules. No catalyst or outside reagent is needed. In fact, Stoddart finds that synthesis of large assemblies is often easier than that of the components. Synthetic chemistry is ready to undergo a fairly dramatic change, he says. We've become exceedingly adept at synthesizing beautifully large molecules with many chiral centers through the whole game of stitching atoms together and manipulating functional groups in a very elegant way. I think what we see this catenane as a prototype for is the building of large assemblies molecule by molecule. Stodda...

Total Synthesis of Huge Paly toxin Molecule Achieved at Harvard

If there is a Mount Everest of chemistry, it has to be paly toxin. Every aspect of its study from isolation to structure determination to total synthesis has been a monumental undertaking. Now organic chemistry professor Yoshito Kishi of Harvard University has scaled Everest with the total synthesis of paly toxin carboxylic acid [ J. Am. Chem. Soc. , 111, 7525,7530(1989)]. The extremely poisonous palytoxin, first isolated from a Hawaiian coral, is C 129 H 223 N3 O 54 , and it weighs in at 2680 daltons. Its 64 dissymmetric carbon atoms and six olefinic bonds offer more than one sextillion (10 21 ) possible isomers. As Kishi quipped, That's getting very close to Avogadro's number. The hugeness of this molecule may be one reason why the Division of Polymer Chemistry invited Kishi to describe the synthesis and conformational studies of the compound to them at the national meeting of the American Chemical Society last week in Miami Beach. In its way, palytoxin gives new meaning ...

Selected biochemical techniques as applied to immunology

As an undergraduate back in 1964, I recall naively suggesting to my organic chemistry professor that he should use antibodies to solve the problem of resolving racemic mixtures, His reply was that, even if antisera with such kne specificity could be found, I should reject me idea because it was not ‘real chemistry’. Twenty-live years later, in 1989, it appears that the antibody molecule has gained its rightful place in the repertoire of legitimate reagents. Here, biased by my point of view as a haematologist who still tries to work in the laboratoty, I have sought to direct the reader’s attention to a broad range of techniques that could be useful to the immunologist or anyone else who uses immunological tools. Some of the titles might appear to be restricted to a harrow aspect of a particular speciality, but they were chosen to illustrate a method of wider application, or propose a solution to a general problem. A topic as broad as that given in the title must be brought into focus, and so I will review selected papers on the fractionation of cell subpopulations, enrichment of plasma membrane domains, novel uses of antibodies to purify proteins, and improvements in the immunodetection of proteins.

Acridine groups used in molecular tweezers

In a contribution to the broad field of molecular recognition, chemists at the University of Illinois, Urbana, have been working on construction of molecular tweezers. Describing these compounds at an organic chemistry session, they noted that the compounds feature planar complexing groups held syn-cofacial (face-to-face with matching of corresponding functional groups) by rigid spacers. Such molecules might be useful in studying intercalation (sandwiching) of such flat species as bases of deoxyribonucleic acids for studies in sequence recognition, carcinogenesis, and chemotherapy. Organic chemistry professor Steven C. Zimmerman told his audience that the term molecular tweezers was coined 10 years ago by organic chemistry professor Howard Whitlock at the University of Wisconsin, Madison. But Zimmerman's compounds show very efficient complexing owing to the recognition that the cavity between the tweezer jaws must be preorganized. The principle of preorganization of host molecules to accommodate guests ar...

Computer journal aims at organic chemists

A journal devoted to application of computer science to organic chemistry has been announced by Pergamon Press. Tetrahedron Computer Methodology , whose first issue will appear within weeks, will consist of three floppy diskettes as well as the printed copy. The diskettes will contain such supplemental materials as runnable programs, program listings, tables of parameters, and atomic coordinates of molecules that complement papers in the printed text. The diskette material will enable the reader to repeat demonstrations described in the paper, apply programs to his or her own work, and verify at once that the techniques perform as the author claims. Referees also will be able to review papers by actual use. Diskettes can be run on IBM PC and PS/2 or compatible microcomputers. The new journal will publish papers, communications, reviews of research topics and of software, and news items. Papers will appear in as little as 90 days after submission, says organic chemistry professor ...

Methyl group with bonding anomaly discovered

Three research groups in the U.S. and Switzerland have discovered a compound with a methyl group whose carbon-hydrogen bonds are virtually eclipsed with three adjacent single bonds [ Angew. Chem. , 99 , 1216 (1987)]. The explanation advanced by the groups for this seemingly unfavorable conformation may lead to better understanding of why enzymes show stereochemical preferences in activation of C-H bonds of substrates. The compound is a tricyclic orthoamide of general structure CH 3- C(NR 2 ) 3 . In particular, organic chemistry professor Gary R. Weisman and graduate student Van B. Johnson of The University of New Hampshire, Durham, made 13-methyl-l,5,9-triazatricyclo[ 7.3.1.0 5,13 ]tridecane. Their original reason for studying this compound was that the nonbonding electron pairs of the nitrogen atoms would be antiperiplanar to (point in the direction opposite from) the C-CH3 bond. Calculations indicated that these nonbonding orbitals would donate electron density into the antibonding σ orbital of the C-CH...

Evidence of three-electron covalent bond firms

Three groups of chemists from Columbia University and Rutgers University have developed evidence for a little-explored form of covalent bonding that may have wide implications in organic chemical reactivity [ J. Am. Chem. Soc. , 109, 7204 (1987)]. The bond in question consists of three shared electrons. The bond turned up initially in studies of chlorine atoms bonded to pyridine nuclei. But the chemists who uncovered this bond type have since found it in other systems. They conclude that it may govern interactions of a wide variety of free radicals with electron-pair donors. The discovery of the unusual pyridine-chlorine bond began with efforts by organic chemistry professor Ronald C. Breslow and postdoctoral fellows Michael Brandl and Jurgen Hunger at Columbia to uncover the reason for highly selective chlorination of steroids esterified with nicotinic or isonicotinic acids [ J. Am. Chem. Soc. , 109, 3799 (1987)]. This work, supported by the National Science Foundation, may be useful for commercial, nonf...

New route to cyclic disulfides developed by Montreal team

A team of chemists at the University of Montreal has developed a method to generate singlet sulfur, S 2 , under conditions mild enough to make cyclic disulfides routinely [ J. Am. Chem. Soc. , 109 , 926 (1987)]. The method may be used to make dithiane antibacterial, antiviral, and anticancer agents and to make dithia analogs of those that are cyclic peroxides. Development of the technique illustrates the value of computer- aided design of reagents. In the method devised by organic chemistry professor Kosta Steliou, such precursors as 2,2'-dibenzoylbiphenyl react with bis(trimethylsilyl) sulfide and boron trichloride to give 2,2'-dithiobenzoylbiphenyl. This compound loses S 2 spontaneously at the 80 to 130 °C reaction temperatures to form 9,10-diphenylphenanthrene. The reaction may involve a dithiacyclobutanophenanthrene intermediate. Dienes like 2,3-diphenylbutadiene can trap the S 2 to yield the Diels-Alder adduct 4,5-diphenyl- 3,6-dihydro-l,2-dithiin in 85% yield. Steliou developed the method with gradu...

ChemInform Abstract: Epoxidation Advance May Spur Its Industrial Use.

AbstractIn Gegenwart von Molekularsieben benötigt man für die asymmetrische Sharpless‐Epoxidation von Allylalkoholen nur noch katalytische Mengen an Titan(IV)‐isopropylat und ( +)‐ bzw. (‐)‐Weinsäure‐diethylester.

Epoxidation advance may spur its industrial use

Asymmetric epoxidation of allylic alcohols finally has been made truly catalytic [ J. Org. Chem ., 51 , 1922 (1986)]. This advance may accelerate industrial use of the reaction to make optically pure intermediates for drugs and pheromones. Engineers at Upjohn already have used the stoichiometric version of the reaction to convert (2 E )-octenl- ol to (3 S )-pentyloxirane-(2 S )-methanol on a multikilo scale. In the future, Upjohn may switch to the catalytic version. Aldrich Chemical offers enantiomers of eight substituted glycidols and their esters made with the catalytic version. And Arco Chemical plans to use it to produce the two enantiomers of glycidol. Invented by organic chemistry professor K. Barry Sharpless at Stanford University in 1980, asymmetric epoxidation uses titanium(IV) isopropoxide and diethyl (+)- or (-)-tartrate to effect reaction of tertbutyl hydroperoxide with allylic alcohol substrates. Chemists can predict and direct the enantiomer to be made by sketching the geometry of the substr...

Method Synthesizes Chiral Boranes In 100% Optical Purity

Chemists at Purdue University have developed a method to hydroborate olefins to chiral boranes in 100% optical purity [J. Am. Chem. Soc., 106, 1797 (1984)]. Processes already exist to convert such boranes to alcohols, amines, and halides, as well as to homologous alcohols, aldehydes, ketones, carboxylic acids and esters, nitriles, cis- and trans-olefins, and acetylenes. Thus the new technique opens routes to absolutely stereospecific synthesis of compounds of nearly every type. In addition, the method regenerates the α-pinene used to induce chirality by a simple displacement, making it almost catalytic in nature and useful for largescale preparations. Moreover, because both enantiomers of α-pinene are available commercially, chemists can choose in advance what chirality the product will have. There were two keys to the success of the technique. First, organic chemistry professor Herbert C. Brown and postdoctoral student Bakthan Singaram discovered that the 2:1 adduct of isopinocampheylborane and tetrameth...

Exit Rates of Micellar Radicals Measured

A nuclear magnetic resonance (NMR) method to measure rates of migration of free radicals out of micelles has been developed by organic chemistry professor Nicholas J. Turro of Columbia University. Because Turro's is an NMR method, it yields detailed structural information on the particular species being investigated. Micelles are assemblies of detergent molecules in water solutions that entrap small, hydrophobic molecules in their interiors. Turro's accomplishment may lead to studies of dynamics of small molecules or reactive intermediates of low concentrations and/or short lifetimes in biological systems. Examples include determining migration rates of intermediates during photoaffinity labeling of biological macromolecules and measuring association and dissociation rates of drug molecules and proteins during transport. Industrial chemists also might use the technique. (For more details on the use of micelles as models of biological systems, see the special report on membrane mimetic chemistry beginning ...

The Two Faces of Chemistry

The promise of better living through chemistry has not always been kept. Chemical techniques were used to produce both penicillin and dynamite, penicillin can have harmful side effects while dynamite has beneficial uses. Insecticides have helped alleviate world hunger while they have disrupted global ecosystems. Numerous petrochemicals have made life both easier and more hazardous.The Two Faces of presents a balanced view, weighing assets and dangers of whole range of modern chemical compounds and their byproducts, including food additives, natural foods, fertilizers, pesticides, drugs and other medications, cosmetics, soaps and detergents, plastics, artificial rubber, fluorocarbons, and leaded gasoline. Caglioti, an organic chemist who has written widely in popular press, not only makes all this material clear and understandable to readers without technical background but also captures drama that accompanied development of new products and revelation, often years later, that they could lead to devastating results. In each case - for example, in his accounts of the saccharin mess and the Pill - he carefully sifts through all accumulated layers of controversy in order to arrive at an unbiased evaluation and assessment of risk.The book's coverage is worldwide, but most of data is taken from those countries that use chemicals intensively: United States, Western Europe, and Japan.The writer and chemist Primo Levi, states in his Foreword that underneath statistics and technical data, which with good reason are plentiful, there flows through this book a silent current of wisdom, educational intent, and morality. While it does not attempt to dictate solutions, by its very character it teaches us how best to go about finding them.Luciano Caglioti is Professor of Organic Chemistry at University of Rome.

Polyhedrane syntheses hotly pursued

The synthesis of dodecahedrane, the last of the classical uniform convex polyhedranes, has been accomplished by organic chemistry professor Leo A. Paquette and his coworkers at Ohio State University, Columbus [ J. Am. Chem. Soc. , 104, 4503 (1982)]. This achievement opens the doors to comparisons of dodecahedrane's actual properties with those calculated for it, and to studies of this and related systems in ways that likely will advance knowledge of the fundamental nature of organic compounds. There also are predictions that substituted dodecahedranes may be useful as drugs. And there is a certain beauty, in that chemists have expressed in hydrocarbon structures the geometrical forms that ancient Greek philosophers related to the basic structure of the universe. The dodecahedrane molecule is a regular 20-carbon polyhedron with 12 pentagonal sides. Paquette made 1,16-dimethyldodecahedrane in late 1980. Of the other hydrocarbons based on Platonic solids, cubane was made by Philip E. Eaton at the University ...

Syntheses of linear tetracyclic antibiotics--tetracyclines and anthracyclines.

Medicinal Research ReviewsVolume 1, Issue 1 p. 23-72 Article Syntheses of linear tetracyclic antibiotics—tetracyclines and anthracyclines Tetsuji Kametani, Tetsuji Kametani Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980, Japan Tetsuji Kametani was born in Tokyo in 1917 and graduated from the Pharmaceutical Institute, Tokyo Imperial University, in 1943. He obtained his Ph.D. from Tkyo Univrsity in 1951. He has been Professor of Organic Chemistry at Pharmacceutical Institute, Tohoku University, since 1959. He is working on the total synthesis of physiologically active natural products and heterocyclic compounds. He is not only editor of an international journal, Heterocycles, but was also its founder in 1973. He received the Academic Prize of the Pharmaceutical Society of Japan in 1969, Medal of Honor with Purple Ribbon, “Shiju Hõshõ” in 1979, apan Academy Award, “Nihon Gakushiin Shõ” and Fujihara Prize in 1980.Search for more papers by this authorKeiichiro Fukumoto, Keiichiro Fukumoto Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980, Japan Keiichiro Fukumoto is an Assistant Professor at Pharmaceutical Institute, Tohoku University. He received his Ph.D. from Osaka University in 1964, and the prize of the Pharmaceutical Society of Japan in 1976. His research deals with a total synthesis of alkalids, terpenes, and steroids.Search for more papers by this author Tetsuji Kametani, Tetsuji Kametani Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980, Japan Tetsuji Kametani was born in Tokyo in 1917 and graduated from the Pharmaceutical Institute, Tokyo Imperial University, in 1943. He obtained his Ph.D. from Tkyo Univrsity in 1951. He has been Professor of Organic Chemistry at Pharmacceutical Institute, Tohoku University, since 1959. He is working on the total synthesis of physiologically active natural products and heterocyclic compounds. He is not only editor of an international journal, Heterocycles, but was also its founder in 1973. He received the Academic Prize of the Pharmaceutical Society of Japan in 1969, Medal of Honor with Purple Ribbon, “Shiju Hõshõ” in 1979, apan Academy Award, “Nihon Gakushiin Shõ” and Fujihara Prize in 1980.Search for more papers by this authorKeiichiro Fukumoto, Keiichiro Fukumoto Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980, Japan Keiichiro Fukumoto is an Assistant Professor at Pharmaceutical Institute, Tohoku University. He received his Ph.D. from Osaka University in 1964, and the prize of the Pharmaceutical Society of Japan in 1976. His research deals with a total synthesis of alkalids, terpenes, and steroids.Search for more papers by this author First published: Spring 1981 https://doi.org/10.1002/med.2610010104Citations: 24 AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume1, Issue1Spring 1981Pages 23-72 RelatedInformation

Computer predicts organic reaction products

A computer program has been developed that predicts products of organic reactions from starting materials and conditions, using general principles of organic reaction mechanisms. Organic chemistry professor William L. Jorgensen of Purdue University, West Lafayette, Ind., has completed the phase of program development dealing with base-catalyzed and nucleophilic reactions [ J. Org. Chem ., 45 , 2043 (1980)]. Future program modules will include acidcatalyzed and electrophilic, radical, carbene, thermal pericyclic, and photochemical reactions. Such mechanistically oriented programs may permit prediction of undiscovered reactions. Also, proposed reactions can be evaluated for feasibility and competition from side reactions. The ordering of organic mechanistic principles for the program may also improve the teaching of organic chemistry. Other workers have devised mechanistically based programs for such projects as finding the best mechanism for successive carbonium ion rearrangements from starting materials t...