This Account presents the development of a suite of stereospecific alkyl-alkyl cross-coupling reactions employing nickel catalysts. Our reactions complement related nickel-catalyzed stereoconvergent cross-coupling reactions from a stereochemical and mechanistic perspective. Most reactions of alkyl electrophiles with low-valent nickel complexes proceed through alkyl radicals and thus are stereoa...

Arylmagnesium and -calcium reagents are easily accessible; however, ether degradation processes limit storability, especially of the calcium-based heavy Grignard reagents. Ortho-bound substituents with phosphanyl donor sites usually block available coordination sites and stabilize such complexes. The reaction of bromo-2,6-bis(diphenylphosphanylmethyl)benzene (1a) with magnesium in tetrahydrofur...

The Grignard reaction of 2,3-O-isopropylidene-α-D-lyxo-pentodialdo-1,4-furanoside and benzylmagnesium chloride (or bromide) afforded a non-separable mixture of diastereomeric benzyl carbinols and diastereomeric o-tolyl carbinols. The latter resulted from an unexpected benzyl to o-tolyl rearrangement. The proportion of benzyl versus o-tolyl derivatives depended on the reaction conditions. Benzyl...

Synthesis of 4-(N,N- dimethylamino)-3-aryl-3-butene-2-one, ethyl-5-aryl-4-oxo-4H-pyran-2-carboxylate, ethyl-5-aryl-4-pyridones-2-carboxylate and 5-aryl-3-cyano-5-methyl-2-pyridones (aryl=3-thienyl, 2-furyl) are described.

Thermal epimerization is the key to changing the endo-to-exo ratio of the diastereomeric bornyl and fenchyl Grignard reagents from 67:33 to 96:4 and from 20:80 to 80:20, respectively.

Nucleophilic additions of lithium keto and ester enolates and mono- and bifunctional Grignard reagents to artemisitene provided C-16-derived artemisinin monomers, dimers, trimers, and tetramers whose antimalarial and cytotoxic activities have been evaluated.

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 highly regioselective and enantioselective copper-catalyzed 1,4-conjugate addition of Grignard reagents to linear α,β,γ,δ-unsaturated ketones was developed. The 1,4-addition products were obtained regioselectively in high yields with up to 98% ee.