Synthesis of olefins. Cross-coupling of alkenyl halides and Grignard reagents catalyzed by iron complexes

Abstract

Grignard reagents are coupled with alkenyl halides such as 1-bromopropene and P-bromostyrene in the pres-ence of catalytic amounts of iron(II1) complexes to afford alkenes. This cross-coupling reaction can be employed as a synthetic route for alkenes, in which primary, secondary as well as tertiary alkyl groups like isopropyl, cyclo-hexyl, and tert-butyl Grignard reagents are utilized. The reaction is stereospecific since trans-1-bromopropene affords only trans- butene-2 with methylmagnesium bromide and iron(II1) pivalate. Furthermore, the rearrange-ment of branched alkyl groups such as tert-butyl has not been observed with an iron catalyst. Among various iron(II1) complexes examined, tris(dibenzoylm'ethido)iron(III) is the most effective from the standpoint of rates and deactivation. Product and spectral studies suggest that the active catalyst is a labile iron species derived by reduction of iron(II1) in situ by the Grignard component. High rates of cross coupling are limited by deactivation of the catalyst due to an aging process attributed to aggregation of the active iron species. Several mechanistic schemes are considered for cross coupling including (a) oxidative addition of alkenyl halide to a low valent alkyli-ron species followed by reductive elimination of the cross-coupled product and (b) assistance by reduced iron in the concerted displacement of halide at the alkenyl center by the Grignard reagent. Olefins are produced.from the cross-coupling reaction 1 between Grignard reagents and alkenyl halides in the.pres-