Direct enantio-convergent transformation of racemic substrates without racemization or symmetrization.
Asymmetric reactions that transform racemic mixtures into enantio-enriched products are in high demand, but classical kinetic resolution produces enantiopure compounds in <50% yield even in an ideal case. Many deracemization processes have thus been developed including dynamic kinetic resolution and dynamic kinetic asymmetric transformation, which can provide enantio-enriched products even after complete conversion of the racemic starting materials. However, these dynamic processes require racemization or symmetrization of the substrates or intermediates. We demonstrate a direct chemical enantio-convergent transformation without a racemization or symmetrization process. Copper(I)-catalysed asymmetric allylic substitution of a racemic allylic ether afforded a single enantiomer of an α-chiral allylboronate with complete conversion and high enantioselectivity (up to 98% enantiomeric excess). One enantiomer of the substrate undergoes an anti-S(N)2'-type reaction whereas the other enantiomer reacts via a syn-S(N)2' pathway. The products, which cannot be prepared by dynamic procedures, have been used to construct all-carbon quaternary stereocentres.
Ito
Hajime
H
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan. hajito@sci.hokudai.ac.jp
Kunii
Shun
S
Sawamura
Masaya
M
D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D007700:Kinetics; D013237:Stereoisomerism
D003300:Copper