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Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

ABSTRACT: Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of ?-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step.

SUBMITTER: Bovino MT

PROVIDER: S-EPMC4097818 | biostudies-literature | 2014 Jun

REPOSITORIES: biostudies-literature

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Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

Bovino Michael T MT Liwosz Timothy W TW Kendel Nicole E NE Miller Yan Y Tyminska Nina N Zurek Eva E Chemler Sherry R SR

Angewandte Chemie (International ed. in English) 20140505 25

Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated ...[more]

PMID: 24798697

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