Lithiated chloromethyltrimethylsilane

Lithiated chloromethyltrimethylsilane is a remarkably stable carbenoid [69] and shows exceptional reactivity in insertions into the alkenyl—zirconium bonds of unsaturated zirconacycles. It is the only known carbenoid that will insert into zirconacyclopentadienes... 

Lithiated chloromethyltrimethylsilane as a stable carbenoid could insert into the alkenyl zirconium bond of zirconacyclopentadienes. The zirconacyclohexadienes 48 formed are valuable precursors of such heteroaromatic compounds as phosphinines (phosphabenzenes) 49, as shown in Scheme 11.19 [21],... 

Lithiated chloromethyltrimethylsilane was reported to insert into zircona-cyclopentadienes to give zirconacyclohexadiene derivatives (Eq. 25) [27]. This has been so far the only example of carbenoid insertion into 5-membered met-allacyclopentadienes. 

Reaction of lithiated allylbenzotriazole 452 with chloromethyltrimethylsilane yields silyl derivative 464 which can be further alkylated to give compound 465 (Scheme 76) <1999JOC1888>. Upon heating, product 465 is readily converted to diene 466 via vicinal elimination of benzotriazolyl and silyl substituents. Additions of lithiated silyl derivative 464 to carbonyl groups of aldehydes lead to alcohols 463 which readily eliminate benzotriazole and silane to furnish 2-(l-hydroxyalkyl)butadienes 466 (R1 = 1-hydroxyalkyl). 

Trimethylsilyldiazomethane (96), prepared in excellent yield from chloromethyltrimethylsilane, is now commercially available (Petrarch). Trimethylsilyldiazomethane is readily lithiated and alkylated (equation 40).Synthetic applications of the resultant silyldiazoalkanes (97) have not yet been extensively explored. These might, for instance, react smoothly with acid chlorides to give diazoketones (see Section 1.4.6.1). 

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