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Synthesis 2009(3): 409-423  
DOI: 10.1055/s-0028-1083324
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Bicyclo[3.1.0]hexan-2-ones by Manganese(III) Oxidation in Ethanol

Kentaro Asahia, Hiroshi Nishino*b
a Department of Materials and Life Sciences, Graduate School of Science and Technology, Kumamoto University, Kurokami, Kumamoto 860-8555, Japan
b Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, Kurokami, Kumamoto 860-8555, Japan
Fax: +81(96)3423374; e-Mail: nishino@sci.kumamoto-u.ac.jp;
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Publication History

Received 18 August 2008
Publication Date:
12 January 2009 (online)

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Abstract

N-Propenyl-3-oxobutanamides underwent the manganese(III)-induced oxidative intramolecular cyclization in ethanol to produce 3-azabicyclo[3.1.0]hexan-2-ones in good yields. A similar reaction of propenyl 3-oxobutanoates and S-propenyl 3-oxobutanethioates also gave the corresponding 3-oxa- and 3-thiabicy­clo[3.1.0]hexan-2-ones. The reaction details, the structure determination, and the reaction pathway are described.

Key words

cyclizations - oxidations - radical reactions - bicy­clo[3.1.0]hexanones - manganese(III) acetate

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15

The most stable conformation of 3,4-trans-pyrrolidinone 3a was calculated to be -310.0 kJ/mol by Spartan ’06 based on the PM3 parameter. The calculated dihedral angle between H-3 and H-4 was 128.9˚. On the other hand, the 3,4-cis 3a was -293.1 kJ/mol and the dihedral angle was 27.3˚.