Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 138, Issue 34, Pages 11038-11043Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b05948
Keywords
-
Categories
Funding
- MEXT, Japan
- JSPS
- Grants-in-Aid for Scientific Research [16K05680, 16H01687] Funding Source: KAKEN
Ask authors/readers for more resources
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 spa hybridized carbon atom. In particular, substitution at the chiral spa-hybridized carbon atom of racemic electrophiles has been rarely exploited. To establish an unprecedented enantioselective substitution reaction of racemic electrophiles, enantio convergent 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
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available