Regio- and stereo-selectivity of alkenyl radical ring closure: a theoretical study

Insofar as one of the fundamental objectives of organic synthesis is the construction of complex molecules from simpler ones, the importance of synthetic efficiency becomes immediately apparent and has been well-recognized.1 The increase in molecular complexity2 that necessarily accompanies the course of a synthesis provides a guide (and a measure) of synthetic efficiency. As a goal, one would like to optimally match the change in molecular complexity at each step with reactions of comparable synthetic complexity. Thus, the creation of many bonds, rings, and stereocenters in a single transformation is a necessary (though not sufficient) condition for high synthetic efficiency. The ultimate, perfect match would constitute single-step syntheses. More realistically, especially in view of the desire for general synthetic methods, the combination of mulScott E. Denmark was born in New York in 1953. He obtained an S.B. degree from MIT in 1975 and carried out research with Daniel Kemp and Richard Holm. His graduate studies at the ETH-Zurich with Albert Eschenmoser culminated with the D. Sc. Tech. degree in 1980. That same year he joined the faculty of the University of Illinois at UrbanasChampaign and was promoted to full professor in 1987. In 1991 he was named the Reynold C. Fuson Professor of Chemistry. His research interests are primarily in the invention of new synthetic reactions, structure and reactivity of organoelement reagents, and the origin of stereocontrol in fundamental carbon−carbon bond forming reactions.

Tandem [4+2]/[3+2] Cycloadditions of Nitroalkenes.

Competition methods and scales for alkyl radical reaction kinetics

Molecular Rearrangements of Organosilicon Compounds

Molecular rearrangements of organosilicon compounds

Absolute rate constants for some intermolecular and intramolecular reactions of .alpha.-, .beta.-, and .gamma.-silicon-substituted radicals

Reactivity and selectivity in the cyclization of sila-5-hexen-1-yl carbon-centered radicals

Search for radical rearrangement in organosilicon systems. I. .alpha.-Silyl radicals from silaneophyl systems

Search for radical rearrangement in organosilicon systems. II. Silicon to carbon Ar1-5 and Ar1-6 phenyl shifts

Reduction of halosilanes by organotin hydrides

James W. Wilt

Papers

Absolute rate constants for some intermolecular and intramolecular reactions of .alpha.-, .beta.-, and .gamma.-silicon-substituted radicals

Reactivity and selectivity in the cyclization of sila-5-hexen-1-yl carbon-centered radicals

Search for radical rearrangement in organosilicon systems. I. .alpha.-Silyl radicals from silaneophyl systems

Search for radical rearrangement in organosilicon systems. II. Silicon to carbon Ar1-5 and Ar1-6 phenyl shifts

Reduction of halosilanes by organotin hydrides