Synlett 2015; 26(17): 2413-2417
DOI: 10.1055/s-0035-1560170
cluster
© Georg Thieme Verlag Stuttgart · New York

Intramolecular Carbolithiation of 3-Lithioxy-5-alkenyllithiums as a Platform for Cyclopentanols and Cyclopentanones

Ilhyong Ryu*
a  Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan   Email: ryu@c.s.osakafu-u.ac.jp
,
Go-hei Yamamura
b  Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Satoshi Minakata
b  Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Mitsuo Komatsu
b  Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Haruka Kubo
a  Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan   Email: ryu@c.s.osakafu-u.ac.jp
,
Mitsuhiro Ueda
a  Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan   Email: ryu@c.s.osakafu-u.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 17 May 2015

Accepted after revision: 21 July 2015

Publication Date:
01 September 2015 (online)


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

 
  • References and Notes


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