Alcohols chlorodimethylsilane

Intramolecular Hydrosilation of Allyl and Homoallyl Alcohols. For a detailed description of the intramolecular hydro-silation-oxidation sequence, see 1,1,3,3-tetramethyldisilazane. 1,1,3,3-Tetramethyldisilazane and AA -diethylaminodimethyl-silane are frequently employed for preparation of hydrodimethyl-silyl ethers for the intramolecular hydrosilation of allyl and homoallyl alcohols. Chlorodimethylsilane in combination with a tertiary amine such as triethylamine is another useful reagent for the synthesis of hydrodimethylsilyl ethers, especially for large scale preparations. ... 

Silylation (see also Protection of alcohols) (Bromomethyl)chlorodimethylsilane, 316 /-Butyldimethylchlorosilane, 92 Chloromethyldiphenylsilane, 74 Chloromethyltrimethylsilane, 76 Di-/-butylmethylsilyl trifluoromethanesul-fonate, 95... 

The high selectivity of olefin metathesis with (2a) was key in the formation of diverse nonracemic vinyl cyclopropanes from chiral homoaUyhc alcohols and allyl chlorodimethylsilane in three steps, or allyl trimethylsilane in two steps, giving diastereomerically pnre cis or trans... 

Reductive Friedel-Crafts alkylation Benzylic alcohols obtained from the InClj-catalyzed alkylation with aldehydes can be reduced in situ by a hydrosilane (e.g., chlorodimethylsilane). The latter process is also catalyzed by Lewis acid. 

Alternatively, the substrate has been accessed by a free radical route starting from propargyl alcohol (6)21. The key step is the radical cyclization of 3-[(bromomethyl)dimethylsilyloxy]-l-propyne (7). This in turn is readily available in high yield by treatment of 6 with commercially available (bromomethyl)chlorodimethylsilane and triethylamine in dichloromethane tn the presence of a catalytic amount of 4-dimethylaminopyridine at 20 C. 

Reaction with Allylic Halides, Alcohols, and their Derivatives. Allylation of allyl and propargyl trimethylsilyl ethers as well as benzyl and propargylic alcohol derivatives proceeds in the presence of a catalytic amount of Lewis acids, such as ZnC, TMS(OTf), and B(C6F5)3. Direct substitutions of the hydroxyl group of allylic, ben-zylic, and propargylic alcohols are catalyzed by HN(S02F)2, a rhenium-oxo complex, and InCls (eq 27). A combination of chlorodimethylsilane and allyltrimethylsilane effectively promotes the deoxygenative allylation of aromatic ketones in the presence of a catalytic amount of an indium compound, such as indium trihalide or metallic indium (eq 28). Allylation of cyclic allylic acetates with allyltrimethylsilane can be catalyzed by molecular iodine. ... 

Intramolecular Hydrosilation of Allyl Amines. The amino group of an allyl amine is silylated with chlorodimethylsilane, and then the resulting silazane is subjected to standard platinum-catalyzed cyclization and oxidation steps to form a syn-2-amino alcohol (eq 1). Exclusive formation of the four-membered cyclic product and the high stereoselectivity should be noted. ... 

A hydroxymethyl group can be attached to the (9-vicinal position of any allyl alcohol in a straightforward manner. The first step is to connect an a-halosilyl group to the hydroxyl group using reagents such as (bromomethyl)chlorodimethylsilane or... 

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