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The next cluster of seven procedures is grouped together in line with the longstanding Organic Syntheses tradition of providing preparations of starting materials that play an established role in important structural transformations and/or multistep syntheses. N-FLUOROPYRIDINIUM TRIFLATE, a versatile electrophilic fluorinating agent, is one such material. The companion preparations of 1-CHLORO-1 -(TRICHLOROETHYL)CYCLOPROPANE and METHYL 2-CHLORO-2-CYCLOPROPYLIDENACETATE describe reliable entry to useful three-membered ring building blocks. The next two procedures address the preparation of (+)-(2R,8aS)-10-(CAMPHORYLSULFONYL)OXAZIRIDINE, a selective, aprotic
oxidizing agent of considerable importance, and (-)-D-2,10-CAMPHORSULTAM, a chiral auxiliary that has found substantial use in asymmetric reactions of various types. A high-yielding, one-step route to highly functionalized sulfonyl acrylates is demonstrated by the preparation of METHYL (Z)-3-(BENZENESULFONYL)-PROP-2-ENOATE, a useful dienophile.
The next six procedures have a strong methodological bent. Thus, the pathway to 4-METHYLTRICYCLO[2.2.2.03-5]OCTANE-2,6-DIONE is based on effective intramolecular oxidative coupling of a bisenolate. The preparation of 3,4-DIHYDRO-(2H)-AZULENONE exemplifies the ability of a diazo ketone to undergo intramolecular cyclization onto an aromatic ring. A concise, four-component condensation forms the basis for a general unsaturated macrolide synthesis as illustrated for 8-PROPIONYL-(E)-5-NONENOLlDE. The practicality of engaging keteniminium salts and chlorocyanoketene in efficient [2+2] cycloadditions is demonstrated by procedures leading to 3-HEXYLCYCLOBUTANONE and 7-CHLORO-7-CYANOBICYCLO[4.2.0]OCTAN-8-ONE. A catalytic means for oxidizing alcohols with oxammonium salts is employed for obtaining (S)-(+)-2-METHYLBUTANAL.
The volume concludes with three convenient procedures to make functionalized molecules having varied applications: 5,$-DIETHOXYBENZOFURAN-4,7-DIONE, 9-n-BUTYL-1,2,3,4,5,6,7,8-OCTAHYDROACRIDIN-4-OL, and ETHYL 3,3-DIETHOXYPROPANOATE.
The long-time standards of Organic Syntheses to provide for use by experimental organic chemists a collection of carefully checked, useful procedures have been extended to this volume thanks to the unstinting efforts of many individuals. Certainly, the members of the Boards of Editors and their students whose names are cited herein gamer a large share of my appreciation for their time-consuming efforts in carrying out the rigorous protocols associated with checking the procedures. The
entire effort has been greatly facilitated by the impressive organizational skills of Professor Jeremiah P. Freeman, the Secretary to the Board. Finally, the production of the final product is largely attributed to his expertise and that of Dr. Theodore W. Greene, our Assistant Editor, whose painstaking efforts with the textual material provide the very attractive and readable text that is before you.
Columbus, Ohio Leo A. Paquette
October 30, 1906 - March 17, 1989
Max Tishler combined, to an exceptional degree, excellence in two seemingly diverse areas. He was a giant in advanced and sophisticated medicinal chemistry research and an administrator with a remarkably inspirational gift for teaching and academic leadership. On the one hand, Tishler pioneered the round-the-clock system for pressure research at Merck. Later, he became the quintessential undergraduate and graduate mentor at Wesleyan University. A distinguished career in industry culminated as President of Merck, Sharpe & Dohme Research Laboratories. Tishler was Editor-in-Chief of Volume 39 of Organic Syntheses, which was published in 1959.
Max Tishler was born in Boston on October 30, 1906. He received the B.S. in 1928 from Tufts College, and the M.A. from Harvard in 1933 while working part-time as a pharmacist. The Ph.D. degree was awarded in 1934 by Harvard. After scientific collaboration with E. P. Kohler and J. B. Conant, he joined Merck & Company, Inc. Research Laboratories in 1937. After retiring from Merck, Dr. Tishler was appointed Professor of Chemistry at Wesleyan University in Middletown, Connecticut (1970 -1972); University Professor of Sciences (1972 - 1975); and Emeritus (1975 - 1989).
Dr. Tishler published more than 100 scientific papers and is cited as an inventor on more than 100 United States patents. A partial list of research contributions include development of processes for the commercial production of vitamin B6, vitamin K, vitamin E, penicillin, streptomycin, and cortisone.
Dr. Tishler was very active in the American Chemical Society, serving for many years on the Board of Directors and as President in 1972. He received the Priestley Medal of the ACS in 1970. He was a member of the National Academy of Sciences. Tishler received an honorary Sc.D. from Tufts University in 1956 and a D.Eng. from Stevens Institute of Technology in 1966. In 1987, he received the National Medal of Science.