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A new method for silylation of allyl ethers with chlorosilanes has been developed by the use of Cp 2 TiCl 2 as a catalyst. This reaction proceeds efficiently at −20 °C in THF using n BuMgCl. A plausible reaction pathway via allyltitanocene intermediate was proposed.

A simple procedure for the preparation of new 1-, 2- and 1,3-chirally substituted indenes is described in which indenyllithium or 2-indenylmagnesium bromide is reacted with a β-pinenyl derived chlorosilane. Synthesis of the ethylene bridged bis(indene) analogues of two of the new compounds is also described.

A catalytic cyclodimerization of arylidene malononitriles proceeded diastereoselectively with reversible redox between vanadium and zinc in the presence of chlorotrimethylsilane. The reductive coupling reaction strongly depended on the co-reductant, additive, solvent, and substrate.

The scope of chromium(II)/cobalt(I)-catalyzed Takai–Utimoto reactions was extended to substrates with unprotected reactive functional groups. In the presence of a higher chlorosilane and manganese the first chromium(II)/cobalt(I)-catalyzed version for the coupling of oxoalkylhalides with aldehydes resulted.

In situ treatment (−78°C) of N-methoxymethyl–N-methylformamide and chlorotrimethylsilane with LDA affords synthetically useful yields of the carbamoylsilane. The latter undergoes silyl group exchange at 145°C in the presence of a chlorosilane and CsF.

Bis(cyclopentadienyl)titanium dichloride (Cp 2 TiCl 2 ) exhibits excellent catalytic activity toward the pinacol-type coupling reaction of aliphatic aldehydes with the assistance of zinc powder and chlorosilane.

A new methodology is described for the synthesis of enol esters of acylsilanes, from readily available vinyl esters. A solution of LDA is added to a mixture of an enol ester (preferably sterically congested, with only one α- carboxyl proton, eg 2-ethylhexanoate) and a chlorosilane at −78°C to afford the product.

Intramolecular Diels-Alder reaction of l-azadienes was conducted by heating the α,β-unsaturated amides (2a ∼ d and 6) in the presence of trimethyl- chlorosilane, triethylamine and zinc chloride to give benzo- and indolo[a]- quinolizidines (5a ∼ e and 7).

Zusammenfassung Perchlorobutenyne 1 react with the methaneimines 2 to give the N-alkylidene-ynamines 3 . The trichlorovinyl group of 3a is transformed by butyllithium and a chlorosilane into a silylethinyl moiety (see 3a → 4 ). Some Cycloadditions of 3 and 4 are described.

The role of Me3SiCl to accelerate the conjugate addition of organocopper reagents has been examined by comparison of the stereochemical results of reactions with 6- and 2,6-disubstituted cyclohexenones, and mechanism involving an initial coordination of the chlorosilane to enones has been proposed.

Chloroplatinic acid catalyzed hydrosilylation of 2-Methyl-1-buten-3-yne with chlorosilanes is reinvestigated; the results can't be satisfactorily explained by Chalk and Harrod mechanism.