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DOI: 10.1055/s-0035-1560170
Intramolecular Carbolithiation of 3-Lithioxy-5-alkenyllithiums as a Platform for Cyclopentanols and Cyclopentanones
Publication History
Received: 17 May 2015
Accepted after revision: 21 July 2015
Publication Date:
01 September 2015 (online)
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Abstract
Intramolecular carbolithiation of 3-lithioxy-5-hexenyllithiums was studied. Unlike the case of 5-hexenyllithium, the cyclization of 3-lithioxy-5-hexenyllithium was very sluggish. Acceleration was observed when lithium chloride was added, suggesting that intramolecular lithioxy coordination would hinder the cyclization. Introduction of a silyl or thiophenyl group at the olefin terminus caused smooth cyclization. The resulting dianions having a cyclopentane framework are subjected to C–C bond-forming reaction with electrophiles to give 3-substituted cyclopentanols. Coupled with the Swern oxidation, the overall protocol served as a platform for 3-substituted cyclopentanones.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1560170.
- Supporting Information
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References and Notes
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For reviews, see:
For selected reviews and recent references on the intramolecular carbolithiation leading to five-membered rings, see:
For reviews on the asymmetric intramolecular carbolithiation in the presence of (–)-sparteine, see:
For our work on ketone α,β-dianions, see:
For conversion of acyllithium into lithium enolates, see: