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Synthesis 2005(19): 3463-3467  
DOI: 10.1055/s-2005-918458
PAPER
© Georg Thieme Verlag Stuttgart · New York

The Origins of Periselectivity and Substituent Effects in Electrocyclizations of o-Nitrosostyrenes: A Computational Study

Andrew G. Leach*a, K. N. Houk*b, Ian W. Davies*c
a AstraZeneca Pharmaceuticals, Mereside, Alderley Park, Macclesfield, SK10 4TG, UK
e-Mail: andrew.leach@astrazeneca.com;
b Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095-1569, USA
e-Mail: houk@chem.ucla.edu;
c Department of Process Research, Merck and Co., Inc., PO Box 2000, Rahway, NJ 07065-0900, USA
e-Mail: ian_davies1@merck.com;
Further Information

Publication History

Received 15 September 2005
Publication Date:
14 November 2005 (online)

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Abstract

Density functional theory has been used to study four pericyclic, or pseudopericyclic, reactions that may be involved in the reductive transformation of o-nitrostyrenes to indoles. These are two electrocyclizations and two 1,5-hydride shifts. The reactions of substituted examples show computed relative barrier heights in agreement with experimental observations.

Key words

pericyclic reactions - indoles - electrocyclic reactions - rearrangements - substituent effects

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