Enantioselective Copper-Catalyzed Carboetherification of Unactivated Alkenes

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 efficie...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2014-06, Vol.53 (25), p.6383-6387
Main Authors: Bovino, Michael T., Liwosz, Timothy W., Kendel, Nicole E., Miller, Yan, Tyminska, Nina, Zurek, Eva, Chemler, Sherry R.
Format: Article
Language:English
Subjects:
Alcohols
Alkenes
Alkenes - chemistry
asymmetric catalysis
Asymmetry
Bioactive compounds
Biocompatibility
Bonding
Catalysis
Chemical synthesis
Copper
Copper - chemistry
Crystallography, X-Ray
Cyclization
Enantiomers
enantioselectivity
Ethers - chemistry
heterocycles
Joining
Mathematical analysis
Molecular Structure
Stereochemistry
Stereoisomerism
Synthesis
Tetrahydrofuran
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Summary: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, 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. A general scheme: A highly enantioselective copper‐catalyzed carboetherification of 4‐pentenols has been developed. Both intramolecular (formal CH functionalization) and intermolecular (net alkyl Heck‐type coupling; see scheme) CC bond formation can occur, thus forming a range of chiral functionalized tetrahydrofurans. DFT transition‐state calculations provide a rationale for the observed asymmetric induction.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201402462