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Lewis base catalysis of bromo- and iodolactonization, and cycloetherification.

ABSTRACT: Lewis base catalyzed bromo- and iodolactonization reactions have been developed and the effects of catalyst structure on rate and cyclization selectivity have been systematically explored. The effects of substrate structure on halolactonization reactions and the interaction of those effects with the effects of catalyst structure have been investigated, leading to synthetically useful improvements in cyclization selectivity. The knowledge acquired was applied to the development of Lewis base catalyzed bromo- and iodocycloetherification reactions. The ability of some of the surveyed catalysts to influence the cyclization selectivity of halolactonization reactions demonstrates their presence in the transition structure of the product-determining cyclization step. This observation implies that chiral derivatives of these catalysts have the potential to provide enantioenriched products regardless of the rates or mechanisms of halonium ion racemization.

SUBMITTER: Denmark SE

PROVIDER: S-EPMC2996424 | biostudies-literature | 2010 Nov

REPOSITORIES: biostudies-literature

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Lewis base catalysis of bromo- and iodolactonization, and cycloetherification.

Denmark Scott E SE Burk Matthew T MT

Proceedings of the National Academy of Sciences of the United States of America 20100812 48

Lewis base catalyzed bromo- and iodolactonization reactions have been developed and the effects of catalyst structure on rate and cyclization selectivity have been systematically explored. The effects of substrate structure on halolactonization reactions and the interaction of those effects with the effects of catalyst structure have been investigated, leading to synthetically useful improvements in cyclization selectivity. The knowledge acquired was applied to the development of Lewis base cata ...[more]

PMID: 20705900

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