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

DOI

10.1139/v03-209

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.

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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