Palladium-Catalyzed Silastannation of Secondary Propargylic Alcohols and their Derivatives

Abstract

A series of terminal propargylic alcohols and their derivatives were subjected to Pd-catalyzed silastannation. In all reactions, complete regio- and stereoselectivities were observed with the tributyltin moiety exclusively adding to the internal carbon of the triple bond in a cis fashion, including the first example of a diyne bis-silastannation. Silastannation reaction products could sequentially be protiodesilylated or iododestannylated, thus providing synthetic routes to 1,1-gem-disubstituted alkenylstannanes and iodides, respectively.

Key words

palladium - catalysis - propargylic alcohols - silastannation - iododestannylation - Stille reaction

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28

At 1 atm, 1 mole of ideal gas has a volume of approximately 23 L. Therefore, considering acetylene as an ideal gas, 1 L of acetylene should correspond to app. 43 mmol. This need not to be more accurate, as long as an excess of acetylene relative to BuLi is assured.

36

Diyne 1j was prepared according to the general procedure with the modification that 25 mmol of ethyl benzoate was treated with 55 mmol of lithium acetylide.

41

A satisfactory elemental analysis could not be obtained due to the presence of an inseparable amount (<5%) of dibenzylideneacetone (dba).