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Synthesis 2003(14): 2241-2248  
DOI: 10.1055/s-2003-41076
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart · New York

Sulfinyl Homo- and Hetero-Dienes from Sulfenic Acids: An Approach Towards Six-membered Nitrogen Heterocycles in Enantiomerically Pure Form

Maria C. Aversa*, Anna Barattucci, Maria C. Bilardo, Paola Bonaccorsi*, Placido Giannetto
Dipartimento di Chimica organica e biologica, Università degli Studi di Messina, Salita Sperone 31 (vill. S. Agata), 98166 Messina, Italy
Fax: +39(090)393895; e-Mail: aversa@unime.it;
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Publication History

Received 6 August 2003
Publication Date:
24 September 2003 (online)

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Abstract

Two different synthetic pathways are presented that provide access to enantiopure sulfinyl hydrazones; in both addition of sulfenic acid/unsaturation represents the crucial step of the procedure. The obtained results are discussed in terms of regioselectivity in the formation of α- and/or β-sulfinyl α,β-unsaturated products when sulfenic acids are reacted with substrates showing carbonyl conjugated triple bonds, and/or their derivatives. Despite its structural limitations, (R S,E,E)-2-[(1S)-isoborneol-10-sulfinyl]-2-butenal dimethylhydrazone (6) behaves as 1-azabuta-1,3-diene in hetero Diels-Alder reaction with N-methylmaleimide, giving a unique cycloadduct with complete endo and facial selectivities.

Key words

1-aza-1,3-dienes - chiral auxiliaries - stereoselective synthesis - sulfenic acids - sulfoxides

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16

In CD3CN solution, H-1 and H-2 resonate as two doublets at δ = 7.05 and 6.83 respectively with J 1,2 = 9.5 Hz.