Synthesis 2016; 48(17): 2823-2828
DOI: 10.1055/s-0035-1561627
special topic
© Georg Thieme Verlag Stuttgart · New York

Iron-Catalyzed Reductive Metalation–Allylation and Metalative Cyclization of 2,3-Disubstituted Oxetanes and Their Stereoselectivity

Yu-ki Sugiyama
a  Department of Materials and Life Chemistry, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686, Japan
b  Anan Institute of Technology, Anan College, 265 Aoki Minobayashi, Anan, Tokushima, 774-0017, Japan   Email: okamos10@kanagawa-u.ac.jp
,
Shiori Heigozono
a  Department of Materials and Life Chemistry, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686, Japan
,
Kazuhiro Tamura
a  Department of Materials and Life Chemistry, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686, Japan
,
Sentaro Okamoto*
a  Department of Materials and Life Chemistry, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686, Japan
› Author Affiliations
Further Information

Publication History

Received: 14 March 2016

Accepted after revision: 31 March 2016

Publication Date:
12 May 2016 (online)

Abstract

A novel process for the reductive magnesiation of 2-substituted oxetanes and the metalative cyclization of ω-alkynyl oxetanes is developed using n-propylmagnesium chloride in the presence of an iron catalyst. The generated intermediate organomagnesium compounds react with electrophiles. The reactions of 2,3-disubstituted oxetanes and their subsequent allylation with allyl halides in the presence or absence of copper(I) cyanide as the catalyst is studied with a unique switching of stereoselectivity being observed in the absence or presence of copper(I) cyanide . In addition, it is found that the metalative cyclization of 3-substituted 2-alkynyl oxetanes proceeds in an anti-selective manner starting from both syn- and anti-substrates. In all cases, the stereochemistry at the 2-position of the oxetanes is lost during the reactions suggesting the involvement of a radical process.

Supporting Information

 
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