Solvolysis of specifically C-6 deuterated 7-halonorbornyl brosylates; stereoselectivity of proton loss for "E1-like" 1,3-elimination in locked bicyclo[2.2.1]heptyl Systems

We have solvolyzed the syn-7-chloro-endo-6-d, anti-7-chloro-endo-6-d, syn-7-chloro-exo,exo-5,6-d 2 , anti-7-chloro-exo,exo-5,6-d 2 , syn-7-bromo-endo-6-d, and anti-7-bromo-endo-6-d norbornyl brosylates 1c, 2c, 1d, 2d, 1e, and 2e in 80:20 ethanol–water buffered with NaOAc, isolated the 3-halonortricyclenes, the products of 1,3-elimination, and assayed for deuterium mass spectrometrically. Analysis of the deuterium-loss data established that …