On the Origin of cine-Substitution in the Stille Coupling of Trisubstituted Iodoalkene and trans-Vinylstannane

Abstract

Factors determining the course of reaction (i.e., usual coupling vs. abnormal cine-substitution) in the Stille coupling of trisubstituted iodoalkene and trans-vinylstannane were investigated. The palladium-catalyzed reaction with triphenylarsine and lithium chloride in N-methylpyrrolidone gave the normal Stille coupling product in good yield and good selectivity, while the use of N,N-diisopropylethylamine and cuprous iodide in toluene afforded the cine-substituted product exclusively. It is proposed that transmetalation between vinylpalladium and vinylstannane species determines the course of reaction.

Unified metal-free intermolecular Heck-type sulfonylation, cyanation, amination, amidation of alkenes by thianthrenation

“…Comparably, cine-substitution of Heck reaction are less investigated. Over the past decades, transition-metal-catalyzed Heck-type cine-arylation and vinylation of electron-deficient alkenes bearing a leaving group have been developed [10][11][12][13][14][15][16][17][18] . Straightforward and environmentally benign Heck-type methods that transform alkenes into versatile carbon electrophiles would be highly desirable 19,20 .…”

Unified Metal-Free Regioselective Heck-Type Sulfonylation, Cyanation, Amination, Amidation of Alkenes by Thianthrenation

“…Over the past decades, transition-metal-catalyzed Heck-type cine-arylation and vinylation of electron-deficient alkenes bearing a leaving group have been developed. [10][11][12][13][14][15][16][17][18] Straightforward and environmentally benign Heck-type methods that transform alkenes into versatile carbon electrophiles would be highly desirable. 19,20 In particular, alkenyl sulfones, alkenyl nitriles, enamines, and enamides are of importance in pharmaceuticals, biochemistry, and materials sciences.…”

“…Comparably, cine-substitution of Heck reaction are less investigated. Over the past decades, transition-metal-catalyzed Heck-type cine-arylation and vinylation of electron-deficient alkenes bearing a leaving group have been developed [10][11][12][13][14][15][16][17][18] . Straightforward and environmentally benign Heck-type methods that transform alkenes into versatile carbon electrophiles would be highly desirable 19,20 .…”