Stereochemical dissection of a carbene fragmentation reaction

Article abstract of DOI:10.1021/ja00050a018

The fragmentation of (S)-3-(2-butoxy)-3-chlorodiazirine (9) in acetonitrile proceeds via N₂ loss to (5)-2-butoxy-chlorocarbene (10) and thence via CO scission to a 2-butyl cation/chloride anion pair (11) that collapses to (5)-2-chlorobutane (12) with ～56% net retention. In 1-butanol, ion pair 11 affords 55% chloride 12 by ion pair return with 82% net retention and 45% of (R)-2-butyl 1-butyl ether (13) by ion pair solvolysis with ～71% net inversion.