Tandem cycloaddition chemistry of nitroalkenes: Probing the remarkable stereochemical influence of the Lewis acid

Scott E Denmark, Mark Seierstad

Research output: Contribution to journalArticle

Abstract

The influence of several Lewis acids on the stereochemical course of the [4 + 2] cycloaddition of nitroalkene 1 and chiral, nonracemic propenyl ether 8 has been examined. All of the Lewis acids examined favored ul relative diastereoselection ('exo' approach); TiCl4, TiBr3(Oi-Pr), SnCl4, and ATPh were the most selective. Within the titanium-based Lewis acids, it was found that increasing the halide-to-alkoxide ratio increased the degree of ul (relative) selectivity, as did switching from chloride to bromide. The internal diastereoselectivity was also dependent on the Lewis acid; most titanium isopropoxide-halides (bromide and chloride) and SnCl4 were highly selective for (1,3-lk) approach, with the selectivity increasing with increasing halide content. Two aluminum-based Lewis acids (MAPh and ATPh) were selective for the opposite sense of internal diastereoselection. The high lk (relative) diastereoselectivity observed only with TiCl2(Oi-Pr)2 is proposed to arise either from Coulombic stabilization of an endo approach or precomplexation of the vinyl ether to the Lewis acid. The switch in internal diastereoselectivity seen in the exo manifold is thought to arise from subtle changes in the steric nature of the Lewis acid-nitroalkene complex.

Original languageEnglish (US)
Pages (from-to)1610-1619
Number of pages10
JournalJournal of Organic Chemistry
Volume64
Issue number5
DOIs
StatePublished - Mar 5 1999

ASJC Scopus subject areas

  • Organic Chemistry

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