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.

authors

Denmark SE,Burk MT

doi

10.1073/pnas.1005296107

subject

Has Abstract

pub_date

2010-11-30 00:00:00

pages

20655-60

issue

48

eissn

0027-8424

issn

1091-6490

pii

1005296107

journal_volume

107

pub_type

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