Halogenation of Optically Active Tertiary Carbinols

Solvent effects on the steric course of the solvolysis of tertiary acyclic derivatives

“…Catalytic hydrogenation afforded (S)-tetrahydrolinalool (1) 10 having 78.8% ee. The alcohol was converted to the chloride 2 (77.4% ee) with SOCl 2 in the presence of Et 3 N. 11 The chloride 2 was configurationally stable at room temperature, but racemized upon exposure to traces of acid. The absolute configuration was determined to be (R) on the grounds of the optical rotation {[α] D 20 = Ϫ0.49 (neat, for 77% ee); lit.…”

Stereospecific nucleophilic substitution at tertiary and quaternary stereocentres

“…The rst hint that a tertiary carbinol could be transformed into its chloro-analogue with some transfer of stereochemical information dates back to the pioneering work of Stevens and McNiven in 1939. 6 Following this preliminary investigation, the steric course of methanolysis of enantiomerically enriched tertiary alkyl chloride 1 was then investigated by Ingold, Hughes and coworkers. 1a Although the absolute conguration of 1 was unknown at that time, the nucleophilic substitution provided 2 with 34% optical activity (Scheme 2).…”

Chemistry of Tertiary Carbon Center in the Formation of Congested C−O Ether Bonds

“…To accomplish substitution reactions with retention, chiral rigid multi‐cyclic electrophiles are sometimes employed [30] . Despite significant research on nucleophilic substitution reactions for the synthesis of ethers, a reaction with inherent reactivity and stereoselectivity (especially retention) of tertiary carbon atoms has not yet been established [31–34] (Scheme 1 B).…”