Catalytic Asymmetric C[BOND]N Bond Formation: Phosphine-Catalyzed Intra- and Intermolecular γ-Addition of Nitrogen Nucleophiles to Allenoates and Alkynoates


  • This research has been supported by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM57034), the Natural Sciences and Engineering Research Council of Canada (postdoctoral fellowship for R.J.L.), the Laboratoire de Synthèse Organique, CNRS UMR 7652, Ecole Polytechnique DCSO, F91128 Palaiseau, France (fellowship for C.M.), and the Croucher Foundation (postdoctoral fellowship for Y.K.C.). We thank Shoshana Bachman for a preliminary study.


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Pin the amine on the gamma: A new method has been developed for the γ-addition of nitrogen nucleophiles to γ-substituted alkynoates or allenoates through intra- and intermolecular processes that are catalyzed by spirophosphine 1 (see scheme). An asymmetric version of this reaction affords enantioenriched pyrrolidines, indolines, and γ-amino-α,β-unsaturated carbonyl compounds.