Organic Letters
Letter
cis-allylation19 with allyltrimethylsilane afforded functionalized
THF 20 in 80% yield with dr ≥ 95:5.
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In summary, we have described an efficient synthesis of
functionalized γ-lactones via Sakurai exo-cyclization/rearrange-
ment of 3,3-bis(silyl) enol esters with a tethered acetal. While the
steric and electronic effects of geminal bis(silane) favor the
desired Sakurai pathway, the methoxy species formed in the
deprotection step facilitates both cyclization and rearrangement.
We have demonstrated the synthetic value of this approach by
efficiently transforming the E-vinylsilane into enyne and the γ-
lactone moiety into multisubstituted THF. Studies of further
applications of this method are underway.
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ASSOCIATED CONTENT
* Supporting Information
■
S
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Experimental procedures, spectral data for products, and X-ray
data of 14. These materials are available free of charge via the
AUTHOR INFORMATION
Corresponding Authors
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful for financial support from the NSFC (21172150,
21321061, 21290180), the NCET (12SCU-NCET-12-03), and
the Sichuan University 985 project.
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