title: Enantioconvergent Nucleophilic Substitution Reaction of Racemic Alkyne-Dicobalt Complex (Nicholas Reaction) Catalyzed by Chiral Brønsted Acid.
abstract: Catalytic enantioselective syntheses enable a practical approach to enantioenriched molecules. While most of these syntheses have been accomplished by reaction at the prochiral sp(2)-hybridized carbon atom, little attention has been paid to enantioselective nucleophilic substitution at the sp(3)-hybridized carbon atom. In particular, substitution at the chiral sp(3)-hybridized carbon atom of racemic electrophiles has been rarely exploited. To establish an unprecedented enantioselective substitution reaction of racemic electrophiles, enantioconvergent Nicholas reaction of an alkyne-dicobalt complex derived from racemic propargylic alcohol was developed using a chiral phosphoric acid catalyst. In the present enantioconvergent process, both enantiomers of the racemic alcohol were transformed efficiently to a variety of thioethers with high enantioselectivity. The key to achieving success is dynamic kinetic asymmetric transformation (DYKAT) of enantiomeric cationic intermediates generated via dehydroxylation of the starting racemic alcohol under the influence of the chiral phosphoric acid catalyst. The present fascinating DYKAT involves the efficient racemization of these enantiomeric intermediates and effective resolution of these enantiomers through utilization of the chiral conjugate base of the phosphoric acid.
authors.affiliation: Department of Chemistry and ‡Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University , Aoba-ku, Sendai 980-8578, Japan.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Terada
authors.affiliation: Department of Chemistry and ‡Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University , Aoba-ku, Sendai 980-8578, Japan.
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Ota
authors.affiliation: Department of Chemistry and ‡Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University , Aoba-ku, Sendai 980-8578, Japan.
authors.forename: Feng
authors.initials: F
authors.lastname: Li
authors.affiliation: Department of Chemistry and ‡Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University , Aoba-ku, Sendai 980-8578, Japan.
authors.forename: Yasunori
authors.initials: Y
authors.lastname: Toda
authors.affiliation: Department of Chemistry and ‡Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University , Aoba-ku, Sendai 980-8578, Japan.
authors.forename: Azusa
authors.initials: A
authors.lastname: Kondoh