Copper(I) catalysts for the diastereoselective radical cyclisation of N‐chloro‐N‐pentenylamines have been developed. The stereoselectivity of the cyclisation depends upon the ligands employed, proving that the radical is bound to the catalyst during the formation of the new stereocentre and making a catalyst‐influenced stereoselective radical reaction possible. The influence of the catalyst on the Beckwith−Houk transition states is discussed. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Unsaturated N-chloroamines cyclise under acidic conditions without addition of a starter for a radical reaction. Therefore it can be concluded that, under the conditions published to date in the literature, the reaction at least partially proceeds via a polar reaction mechanism rather than via free radicals.

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