Synergic effect of vicinal stereocenters in [3 + 2] cycloadditions of carbohydrate azadipolarophiles and mesoionic dipoles: Origin of diastereofacial selectivity

M. Avalos, R. Babiano, P. Cintas, F. R. Clemente, R. Gordillo, J. L. Jiménez, J. C. Palacios

Research output: Contribution to journalArticle

22 Scopus citations

Abstract

The intermolecular [3 + 2] cycloaddition of carbohydrate-derived 1,2-diaza-1,3-butadienes and 1,3-thiazolium-4-olates provides a conceptual basis for the problem of diastereofacial preference in the acyclic series of unsaturated sugars. Experimental results employing a side chain of D-arabino configuration have shown the stereodifferentiation exerted by the first stereogenic center that renders the Re,Re face of the acyclic sugar-chain azadiene eligible for cycloaddition (J. Org. Chem. 2000, 65, 5089). The results of the present work, now utilizing an alternative framework of D-lyxo configuration, evidence the discriminating power of the second stereogenic carbon, which induces the preferential approach to the Re,Si face of the heterocyclic dipole. This scheme of face selectivity is also grounded in theoretical calculations at a semiempirical level. In addition to dihydrothiophenes, which are the expected products of the [3 + 2] cycloaddition, bicyclic systems based on dihydrothieno[2,3-c]piperidine skeleton can also be obtained.

Original languageEnglish (US)
Pages (from-to)5139-5145
Number of pages7
JournalJournal of Organic Chemistry
Volume66
Issue number15
DOIs
StatePublished - Jul 27 2001

ASJC Scopus subject areas

  • Organic Chemistry

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