1,3-Dipolar cycloaddition of 2-dialkylaminothioisomünchnones with aliphatic aldehydes: Synthesis of β-lactams and thiiranes, structure elucidation, and rationale for chemoselective fragmentation of cycloadducts

Martin Avalos, Reyes Babiano, Pedro Cintas, Fernando R. Clemente, Ruth Gordillo, José L. Jiménez, Juan C. Palacios

Research output: Contribution to journalArticle

11 Scopus citations

Abstract

A series of highly funtionalized β-lactams and thiiranes can be generated on treatment of 1,3-thiazolium-4-olates (thioisomünchnones) with aliphatic aldehydes. Although in some cases a variety of products have been obtained, the present paper now provides a mechanistic rationale to explain the product distribution based on stereoelectronic effects. Thus, ring fragmentation of the initial [3+2] cycloadduct is essentially dictated by the electronic character of the aryl substituent on the nitrogen atom of the parent thioisomünchnone. However, further evolution of such cycloadducts into β-lactams or thiiranes is governed by steric effects to a large extent. Evidence for such interactions has been obtained by computing PM3-optimized diastereomeric transition structures in the reaction of a thioisomünchnone with a chiral aliphatic aldehyde.

Original languageEnglish (US)
Pages (from-to)6338-6348
Number of pages11
JournalJournal of Organic Chemistry
Volume68
Issue number16
DOIs
StatePublished - Aug 8 2003

ASJC Scopus subject areas

  • Organic Chemistry

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