M. Ochiai, K. Sumi, Y. Takaoka
1988
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Journal
Tetrahedron
Abstract
Abstract Alkenyl(phenyl) iodonium tetrafluoroborates 3 were synthesized from alkenylsilanes 1 by the reaction with iodosylbenzene and boron trifluoride-diethyl ether or triethyloxonium tetrafluoroborate. The reaction proceeds stereospecifically with retention of configuration of 1 . X-ray diffraction analysis of (4-tert-butylcyclohexenyl)phenyliodonium tetrafluoroborate ( 3b ) revealed the highly ionic structure with the distorted T-shape arrangement. Iodonium salts 3 behave like the highly activated species of vinyl iodides due to the high leaving ability of the iodine(III) substituents. Thus, a variety of substituted olefins including α-cyano and α-nitro olefins, vinyl sulfides, vinyl halides, and α,β-unsaturated esters, were synthesized from 3 under mild conditions. A ligand coupling mechanism via the formation of 10-I-3 intermediate 27 containing a copper(III) ligand is proposed for the substitutions of 3 with nucleophiles.