Journal
ADVANCED SYNTHESIS & CATALYSIS
Volume 361, Issue 19, Pages 4602-4610Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/adsc.201900665
Keywords
enantioselective hydrogenation; N-O alcohol; TS; mechanism
Categories
Funding
- NSFC [21877025, 41606174]
- Scientific Research Foundation of Hebei Educational Committee [QN2016177, QN2017021]
Ask authors/readers for more resources
Axial N-O alcohols, which have two large carboline moieties connected to the axis were synthesized and used in catalytic enantioselective 1,2- and 1,4-transfer hydrogenations of total 26 ketimines and beta-enamino esters. Excellent levels of enantioselectivity ranging from 91% to 99% were achieved by using catalyst (aS)-(S)-3,3 '-bis((S)-2-(hydroxymethyl)pyrrolidine-1-carbonyl)-9,9 '-dimethyl-9H,9 ' H-[1,1 '-bipyrido[3,4-b]indole] 2-oxide. Interestingly, a mixture of (aS)-(S)-3,3 '-bis((S)-2-(hydroxymethyl)pyrrolidine-1-carbonyl)-9,9 '-dimethyl-9H,9 ' H-[1,1 '-bipyrido[3,4-b]indole] 2-oxide and (aR)-(S)-3,3 '-bis((S)-2-(hydroxymethyl)pyrrolidine-1-carbonyl)-9,9 '-dimethyl-9H,9 ' H-[1,1 '-bipyrido[3,4-b]indole] 2-oxide was also able to provide high enantioselectivities up to 95% that is the same as that using pure (aS)-(S)-3,3 '-bis((S)-2-(hydroxymethyl)pyrrolidine-1-carbonyl)-9,9 '-dimethyl-9H,9 ' H-[1,1 '-bipyrido[3,4-b]indole] 2-oxide. A plausible catalytic mechanism was suggested and total four kinds of transition states (TS) including almost 60 TS structures were investigated using density functional theory (DFT) with different basis sets such as 6-311G(2d,p). The predicted activation energy data are consistent with the experimental results.
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