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Intramolecular [4 + 2] Cycloadditions of Iminoacetonitriles: A New Class of Azadienophiles for Hetero Diels−Alder Reactions

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David T. Amos, Adam R. Renslo, and Rick L. Danheiser*

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139

J. Am. Chem. Soc., 2003, 125 (17), pp 4970–4971

DOI: 10.1021/ja034629o

Publication Date (Web): April 4, 2003

Section:

Heterocyclic Compounds (One Hetero Atom)

Abstract

Iminoacetonitriles participate as reactive dienophiles in stereoselective intramolecular hetero Diels−Alder reactions which afford substituted quinolizidines. The cycloadduct with exo-oriented cyano group is obtained as the major or exclusive product of the reaction as a consequence of the α-amino nitrile anomeric effect The α-amino nitrile moieties incorporated in the cycloadducts constitute latent iminium ions, which upon exposure to mild protic or Lewis acids are unmasked, setting the stage for further useful synthetic transformations. For example, reductive decyanation with NaBH₃CN excises the cyano group, while Bruylants reaction with Grignard reagents and acetylides lead to α-substituted amines. The substrates for these [4 + 2] cycloadditions are prepared from readily available alcohols via a Mitsunobu coupling reaction with the previously unknown, easily prepared reagent HN(Tf)CH₂CN followed by cesium carbonate promoted elimination of trifluoromethanesulfinate.

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