Document Type

Article

Publication Date

2004

Publication Title

Canadian Journal of Chemistry-Revue Canadienne De Chimie

Volume

82

Issue

2

First Page

366

Last Page

374

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-Co-4(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.

DOI

10.1139/v03-209

Comments

The article available for download is the authors accepted manuscript. The definitive version is published in the Canadian Journal of Chemistry - Revue Canadienne De Chimie and is available here. Copyright (2012) Canadian Science Publishing.

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