Enantioselective Hydroazidation of Trisubstituted Non‐Activated Alkenes

This is the authors' abstract. We don't add key points for this paper.

A one‐pot procedure for the enantioselective hydroazidation of non‐activated trisubstituted alkenes is described. Hydroboration with monoisopinocampheylborane (IpcBH 2 ) provides dialkylboranes that are in situ selectively converted into monoalkyl‐substituted catecholboranes; these undergo radical azidation upon treatment with benzenesulfonyl azide and a radical initiator. Enantiomerically enriched azides were thus obtained in yields of 59–81 % and enantioselectivities of up to 94:6 e.r. (98:2 e.r. if the intermediate dialkylborane is purified by crystallization). A rapid access to enantiomerically pure (+)‐rodocaine is also described. The use of other arenesulfonyl radical traps enables enantioselective hydroallylation, hydrosulfanylation, and hydrobromination reactions with yields of 71–86 %.