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2.11.8.8.1 Variation 1: Using Grignard or Other Magnesium Reagents

DOI: 10.1055/sos-SD-002-00797

Negishi, E.-i.; Takahashi, T.Science of Synthesis, (20032795.

The CC bond formation reactions of alkynes or alkenes with Grignard reagents catalyzed by zirconium(II)alkene complexes can be classified into seven types of reactions as shown in Scheme 151. The first type is the ethylmagnesation of alkenes (Dzhemilev's reaction)[‌193‌,‌358‌] or alkynes,[‌366‌] e.g. to give 413 and 414, respectively (see also Section 2.11.8.8), the second type is the cyclomagnesation reaction of dienes, e.g. to give 415,[‌362‌] and the third is the cyclodimagnesation of dienes, e.g. to give 416.[‌362‌] The cyclodimagnesation reaction products are very often obtained together with the ethylmagnesation or cyclomagnesation products. The fourth type of reaction is ethylation of allylic compounds, such as the reactions of 417 and 419 to give 418 and 420, respectively.[‌367‌‌369‌] The fifth type is the formation of cyclobutenes such as 421.[‌370‌] The sixth is the cycloal­lylation reaction, e.g. to give 423 from 422, which is a combination of cyclomagnesation and CC bond formation of allylic compounds.[‌372‌,‌373‌] The seventh is alkylation of sty­renes, e.g. formation of 424.[‌371‌]

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