Journal
ACS CATALYSIS
Volume 11, Issue 11, Pages 6733-6740Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c01689
Keywords
enantioselective borylation; copper(I) catalyst; diboron; aminoboronates; DFT calculations
Categories
Funding
- Japan Society for the Promotion of Science (JSPS) via KAKENHI [18H03907, 17H06370, 20H04795, 21H01926]
- JST via CREST [JPMJCR19R1]
- FOREST [PJ2521A021]
- Institute for Chemical Reaction Design and Discovery (ICReDD)
- Grants-in-Aid for Scientific Research [21H01926, 20H04795, 17H06370, 18H03907] Funding Source: KAKEN
Ask authors/readers for more resources
The study introduces a novel catalytic enantioselective nucleophilic borylation reaction of ketimines, leading to the efficient synthesis of optically active alpha-amino tertiary boronates with high enantioselectivity. The products can be further converted into peptidylboronic acid derivatives that are difficult to synthesize by other methods. Density functional theory calculations suggest that noncovalent interactions play a crucial role in determining the enantioselectivity of this reaction.
The catalytic enantioselective nucleophilic borylation of ketimines is reported. A series of acyclic dialkyl ketimines reacted efficiently with bis(pinacolato)diboron in the presence of a copper(I)/chiral N-heterocyclic carbene catalytic system to furnish optically active alpha-amino tertiary boronates with high enantioselectivity (up to 99% ee). The products can be converted into peptidylboronic acid derivatives that bear bulky aliphatic substituents, compounds that are difficult to synthesize by other methods. Density functional theory calculations indicated that the enantioselectivity-determining step involves noncovalent interactions that recognize the prochiral dialkyl ketimine, leading to highly efficient enantiodiscrimination.
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