Phenyl- and ethyl-magnesium bromides undergo regioselective asymmetric allylic substitution with high enantioselectivity under the catalysis of chiral amidophosphane-copper(I) complexes.

Reaction of n-propylamino-N,N-bis(2-methylene-4-tert-butyl-6-methylphenol), H(2)L1, n-propylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol), H(2)L2, and benzylamino-N,N-bis(2-methylene-4-tert-butyl-6-methylphenol), H(2)L3, with anhydrous ferric chloride in the presence of base yields the products, [FeL1(μ-Cl)](2) (1), [FeL2(μ-Cl)](2) (2) and [FeL3(μ-Cl)](2) (3). In the solid state, these com...

The design of compounds suitable for drug development is a multi-dimensional process that requires the ne tuning of molecular properties beyond potency. For instance, physical– chemical properties that directly affect hydrolytic stability and bioavailability of the compound must be addressed to avoid side effects in vivo. Due to the excellent pharmacological prole of uorinated drugs, the str...

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.

Aliphatic ,w-dibromides can be converted to the corresponding c,w-di—Grignard reagents; for those members carrying less than four carbon atoms between the functions, special procedures are required. The synthesis, structure and applications of the di-Grignard reagents are discussed; particular emphasis is placed on the structures of the corresponding cyclic dialkylmagnesiums, and on the use of ...

New developments from our laboratories in Directed ortho (DoM) and remote (DreM) metalation reactions are presented and connections to transition metal catalyzed cross coupling and ole®n metathesis processes are described. As it heads into its seventh decade since the Gilman and Wittig discovery, the Directed ortho metalation (DoM) reaction (Scheme 1) [1] is increasingly poised to the challenge...

[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...

An efficient enantioselective synthesis of lactones was developed based on the catalytic asymmetric conjugate addition (ACA) of alkyl Grignard reagents to pyranones. The use of 2H-pyran-2-one for the first time in the ACA with Grignard reagents allows for a variety of further transformations to access highly versatile building blocks such as β-alkyl substituted aldehydes or β-bromo-γ-alkyl subs...