Silylacetylenic reagents

Diketones. The Sharpless procedure for oxidation of alkenes with NaIO catalyzed by Ru02 (11,462-463) is equally efficient for oxidation of alkynes to 1,2-diones. In fact, alkenes and alkynes react at a similar rate, but ether, epoxide, and ester groups are stable to the reagent. A 1-silylacetylene is oxidized to an acylsilane. Yields are moderate to high.1... 

A silylacetylene was reported to enter the similar nickel-catalyzed reaction [Eq. (8) 51]. However, butadiene gave a cyclic Grignard reagent, rather than the simple allyl... 

N-methylmethoxyamine (Scheme 23). The method appears to be the only one which allows direct conversion of an organolithium reagent into a secondary amine, usually isolated as the benzamide. 5-Amino-2-cyano-4-silylpyrroles can be prepared by the palladium or nickel catalysed condensation of silylacetylenes with trimethyl silyl cyanide (Scheme 24).60... 

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