Dimerization of vinyl Grignard reagents and concomitant alkylation with alkyl halides have been achieved by using Cp(2)TiCl(2) as a catalyst.

Catalytic cross-coupling of aryl Grignard reagents with primary and secondary alkyl halides bearing beta-hydrogens is achieved using Fe(III) amine-bis(phenolate) halide complexes.

Highly regioselective ring-opening coupling reactions of diarylmethylenecyclopropa[b]naphthalenes with Grignard reagents have been developed, which provide differently substituted β-vinylic naphthalenes in moderate to excellent yields.

We describe a general catalytic methodology for the enantioselective dearomative alkylation of pyridine derivatives with Grignard reagents, allowing direct access to nearly enantiopure chiral dihydro-4-pyridones yields up 98%. The involves dearomatization in situ-formed N-acylpyridinium salts, employing alkyl organomagnesium reagents as nucleophiles and copper (I) complex catalyst. Computationa...

The carbomagnesiation of dienes and enynes with sec- and tert-alkyl Grignard reagents has been achieved by using copper salts as catalysts.

Selective functionalization reactions of aromatic and heteroaromatic halides with carbon, oxygen, and nitrogen nucleophiles have attracted much attention in the last decades. In addition to typical metal-catalyzed coupling reactions, direct functionalization of aryl halides through the formation of Grignard reagents offer new ways for the efficient construction of biologically interesting carbo...

[reaction: see text] Treatment of hydroxy-substituted silyl epoxides with Grignard reagents induces a 1,2-carbon shift to reveal alpha-silyl aldehydes, which are trapped by highly diastereoselective addition reactions of the Grignard reagent. The starting epoxides are readily accessible from propargylic alcohols by regio- and diastereoselective hydrosilylation and epoxidation reactions. In addi...

Changing course: While organolithium and Grignard reagents favor addition to C1 of A (R=Me), the corresponding organoytterbium reagents add to C2 (R=tBu). Computational studies provide insights into the nature of organoytterbium species and their reactivity, and a total synthesis of (-)-mansonone B illustrates the utility of the method in terpenoid synthesis. Tf=trifluoromethanesulfonyl.