Synthesis 2015; 47(23): 3805-3812
DOI: 10.1055/s-0035-1560347
paper
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Organocatalytic Michael Addition–Cyclization Cascade of Cyclopentane-1,2-dione with Substituted (E)-2-oxobut-3-enoates

Gert Preegel
a   Department of Chemistry, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, Estonia
,
Kaja Ilmarinen
a   Department of Chemistry, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, Estonia
,
Ivar Järving
a   Department of Chemistry, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, Estonia
,
Tõnis Kanger
a   Department of Chemistry, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, Estonia
,
Tõnis Pehk
b   National Institute of Chemical Physics and Biophysics, Akadeemia tee 23, 12618 Tallinn, Estonia   Email: margus.lopp@ttu.ee
,
Margus Lopp*
a   Department of Chemistry, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, Estonia
› Author Affiliations
Further Information

Publication History

Received: 27 June 2015

Accepted after revision: 28 August 2015

Publication Date:
01 October 2015 (online)


Abstract

An organocatalytic cascade Michael addition-cyclization reaction of cyclopentane-1,2-dione with substituted (E)-2-oxobut-3-enoates, creating two stereocenters and giving bicyclic hemiacetals 3 in excellent yield (up to 93%) and enantioselectivity (up to 96% ee) was developed. From 2-chlorophenyl-substituted (E)-2-oxobut-3-enoate, the adduct revealed pseudo-atropisomerism from the hindered rotation of the phenyl ring. The hemiacetal 3 was reduced with Et3SiH and Lewis acid affording substituted 1,2-cyclopentanedione 8, and disilylated with an excess of TMSOTf and Et3N to the dienol disilyl ether 9.

Supporting Information

 
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