Stereoselective palladium-catalyzed Kumada-Corriu reactions of functionalized alkenyl halides and a variety of Grignard reagents, including those bearing β-hydrogen atoms and sensitive functional groups, can be carried out at room temperature using a new combination of reagents.

A catalyst system able to perform highly enantioselective Cu-catalysed allylic alkylations with Grignard reagents is described.

The mechanism of the previously developed cross-coupling reaction of aryl Grignard reagents with aryl halides was explored in more detail. Single electron transfer from an aryl Grignard reagent to an aryl halide initiates a radical chain by giving an anion radical of the aryl halide. The following propagation cycle consists entirely of anion radical intermediates.

The addition of Grignard reagents to aldehydes in the presence of chiral aminoalcohols shows a moderate enantioselectivity. The study carried out with a series of ligands allows the correlation between the structural characteristics and their reactivity. Introduction The use of chiral aminoalcohol to lead asymmetrically nucleophilic additions of organometallics to carbonyl compounds is a field ...

It is shown that two competitive pathways (T2 vs T4) exist for Grignard reagent formation. While the nonradical pathway T2 leads to retention of the configuration, the radical pathway T4 gives racemization. Our calculations suggest the way that T2 can be enhanced, which should be of significance to prompt new synthesis approaches for the preparation of chiral Grignard reagents.

The use of transition-metal catalysis to form new C C bonds is an important tool in organic synthesis. Palladiumand nickel-catalyzed C C bond-forming reactions have been extensively explored and are well understood. The use of iron as the catalyst has gained much less attention, despite the innovative work of Kochi et al. in the 1970s. Recently, several groups have turned their attention toward...

Well-established, traditional Kumada cross-couplings involve preformed Grignard reagents in dry ethereal solvent that typically react, e.g., with aryl halides via Pd catalysis to afford products of net substitution. Therefore, in the work described, which appears to be counterintuitive, exposure of these same aromatic halides to catalytic amounts of Pd(II) and excess magnesium metal in pure wat...

A new method for the cross-coupling reaction of Grignard reagents with alkyl chlorides, bromides, and tosylates has been developed by the use of a nickel catalyst in the presence of a diene as an additive. This reaction proceeds efficiently at 0-25 degrees C in THF using primary and secondary alkyl and aryl Grignard reagents. Nickel complexes bearing no phosphine ligands, such as NiCl2, Ni(acac...

Grignard reagents are used as intermediates in the production of complex molecules, since they can be to form new carbon-carbon bonds, e.g. formation active pharmaceutical ingredients....

Abstract The cobalt‐catalyzed reaction between 1,3‐dithiolanes and Grignard reagents, for the efficient synthesis of multi‐substituted alkene products, is described. method was applicable to a variety benzylic dithiolane substrates, affording di‐, tri‐, tetra‐substituted 1,1‐diaryl products in good excellent yields. use reagents with aryl aldehyde‐derived enabled access natural product‐derived ...