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. 2009 May 13;131(18):6318-9.
doi: 10.1021/ja8097349.

Phosphine-promoted [3 + 3] annulations of aziridines with allenoates: facile entry into highly functionalized tetrahydropyridines

Hongchao Guo  1 , Qihai Xu, Ohyun Kwon
Affiliations

Phosphine-promoted [3 + 3] annulations of aziridines with allenoates: facile entry into highly functionalized tetrahydropyridines

Hongchao Guo et al. J Am Chem Soc. .

Abstract

The phosphine-mediated [3 + 3] annulations of aziridines and allenes are experimentally simple reactions, run under very mild conditions, for the preparation of highly functionalized tetrahydropyridines in yields of up to 98% and trans/cis ratios of up to 97:3. In addition to steps that are typical of nucleophilic phosphine-catalyzed reactions of allenoates, the mechanism of this new reaction features apparent nucleophilic aromatic substitution and concomitant desulfonylation, processes hitherto unknown during phosphine-promoted cycloaddition reactions. Notably, these reactions are the first reported examples of aziridines as reaction partners in nucleophilic phosphine-catalyzed transformations.

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Figures

Scheme 1
Scheme 1
Deuterium Labeling Experiments
Scheme 2
Scheme 2
Suggested Mechanism for the Formation of Tetrahydropyridine 3
See this image and copyright information in PMC

References

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