The Meyers Reaction (1994-2010)

Abstract

The Meyers reaction, i.e. the nucleophilic aromatic substitution reaction between aryloxazolines with organolithium and organomagnesium reagents is a very efficient and reliable method for the formation of new carbon-carbon and carbon-heteroatom bonds. The aim of this review is to present a general overview of this reaction in chiral and racemic form, emphasizing its scope and limitations. The literature is covered since 1994.

Regio- and Chemoselective Kumada–Tamao–Corriu Reaction of Aryl Alkyl Ethers Catalyzed by Chromium Under Mild Conditions

“…It was revealed that the reaction did not proceed in the absence of chromium­(II) chloride (Table , entry 1). This result suggests that a nucleophilic aromatic substitution with Grignard reagent involving a Meyers-type reaction mechanism can be excluded in the transformation . CrCl 3 displays high reactivity in the promotion of the C–O bond-activation/cross-coupling reaction (entry 3).…”

Sterically Controlled Cu-Catalyzed or Transition-Metal-Free Cross-Coupling of gem-Difluoroalkenes with Tertiary, Secondary, and Primary Alkyl Grignard Reagents

“…The transition-metal-free coupling reaction of organic halides with Grignard reagents is a formidable challenge in the organic synthesis . In addition, a survey of the literature revealed that there were only a few reports on the coupling reaction of organic fluoride with Grignard reagents under transition-metal-free conditions. , However, successful examples of these coupling reactions are limited to substrates containing directing groups. , Encouraged by the above success, we next examined the feasibility of tertiary butylation of gem -difluoroalkene under transition-metal-free conditions. Only a trace amount of Z - 3aa was observed when the reaction was performed in THF without the addition of CuCN at rt (entry 14).…”

Between a reactant rock and a solvent hard place – molecular corrals guide aromatic substitutions

“…These most commonly involve fluorobenzenes substituted with a variety of activating groups, including nitro, cyano, sulfonyl, sulfinyl, bromide, keto, or ester, 8 the mechanisms of which have been characterised both kinetically 9 and theoretically. 10 However, when fluoro and alkoxy groups are on naphthoic acids, carboxyl groups (CO 2 H) usually require protection and subsequent deprotection steps, 11 in processes where they are converted into an oxazoline, 12 a bulky ester, 13 or an imino group. 14 In these systems, alkyl and aryl substitution can now be readily accomplished in generally excellent yields in the absence of a metal catalyst via a nucleophilic displacement of an ortho-fluoro or methoxy group in unprotected naphthoic acids with lithium ion and Grignard reagents.…”