Abstract

Bis(hexacarbonyldicobalt) complexes of benzyl ether – methyl ether or benzyl ether – acetate derivatives of hepta-2,5-diyne-1,7-diols undergo selective Lewis-acid-mediated Nicholas reactions with enol silanes, silyl ketene acetals, and allylstannanes, preferentially replacing the methyl ether or acetate function. Hydride nucleophiles are similarly incorporated selectively using a benzyl ether – alcohol derivative. Subsequent Nicholas reaction at the benzyloxy-bearing site may be accomplished with an identical or a different nucleophile, affording skipped 1,4-diyne-Co4(CO)12 complexes. In instances of lower selectivity for monosubstitution reactions with benzyl ethers, reverting to the use of a menthyl ether – methyl ether complex gives much improved selectivity for methyl ether substitution.Key words: cobalt alkyne complexes, Nicholas reaction, Lewis acids, 1,4-diynes.

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