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Anion Relay Chemistry: An Effective Tactic for Diversity Oriented Synthesis

Amos B. Smith, III* and Ming Xian

*Department of Chemistry, Laboratory for Research on the Structure of Matter, and Monell Chemical Senses Center, University of Pennsylvania, Philadelphia, Pennsylvania 19104, Email:

A. B. Smtih, III, M. Xiang, J. Am. Chem. Soc., 2006, 128, 66-67.

DOI: 10.1021/ja057059w

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A linchpin coupling protocol is based on anion relay chemistry (ARC). The addition of an anion to an epoxide, bearing on a distal carbon a trialkyl silyl group and an anion stabilizing group furnishes upon epoxide ring opening an oxyanion. Addition of HMPA triggers a solvent controlled 1,4-Brook rearrangement leading to a new distal anion, which reacts with various electrophiles.

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proposed reaction pathway

Key Words

Corey-Seebach Reaction, Brook Rearrangement, β-Hydroxy Ketones, 1,3-Dithianes

ID: J48-Y2006-4210