Oxoalkyl-triphenylbismuthonium salts

Scheme 12 Reactions of 2-oxoalkyl- and 3-oxoalkyl-triphenylbismuthonium salts with hetero nucleophiles [33-35]...

Oxoalkyl- and 3-oxoalkyl-triphenylbismuthonium salts transfer the alkyl groups to various hetero nucleophiles such as piperidine, triphenylphosphane, arylsulfinates, alcohols, arylthiolates, dimethyl sulfide, and metal halides under mild conditions (Equation (132)).214 215 Methyl- and allyl-triphenylbismuthonium salts also alkylate some heteronucleophiles.216 The leaving ability of the triphenylbismuthonio group has been found to be higher than that of the triflate anion. 

When treated with a base such as THF at low temperatures, 2-oxoalkyl-triphenylbismuthonium salts are readily converted to bismuthonium 2-oxoalk-ylides, whereas 3-oxoalkyltriphenylbismuthonium salts undergo )8-elimination to afford a, )8-unsaturated ketones and triphenylbismuthine... 

Scheme 5.34. Typical reactions of (2-oxoalkyl)triphenylbismuthonium salts and their derived ylides.

Scheme 5.35. Typical reactions of (3-oxoalkyl)triphenylbismuthonium salt [95JCS(P1)2543].

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