Transition metal-catalyzed hetero-[5 + 2] cycloadditions of cyclopropyl imines and alkynes: dihydroazepines from simple, readily available starting materials

Paul A Wender; Torben M Pedersen; Marc J C Scanio

doi:10.1021/ja0285013

Transition metal-catalyzed hetero-[5 + 2] cycloadditions of cyclopropyl imines and alkynes: dihydroazepines from simple, readily available starting materials

J Am Chem Soc. 2002 Dec 25;124(51):15154-5. doi: 10.1021/ja0285013.

Authors

Paul A Wender¹, Torben M Pedersen, Marc J C Scanio

Affiliation

¹ Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. wenderp@stanford.edu

PMID: 12487573
DOI: 10.1021/ja0285013

Abstract

The first example of a transition metal-catalyzed hetero-[5 + 2] cycloaddition reaction is described. Use of cyclopropyl imines as five-atom components, an alkyne as a two-carbon component, and a Rh(I) catalyst enables a new route to dihydroazepines. This new hetero-[5 + 2] cycloaddition works well with aldimines, ketimines, and with substituted cyclopropanes and affords the desired dihydroazepines in excellent yields as single regioisomers. Use of serial imine formation/aza-[5 + 2] cycloaddition generates the desired dihydroazepines in one operation from three commercially available starting materials. The reaction has been scaled to give gram quantities of dihydroazepine.