TY - JOUR
T1 - Photochemical Deracemization of Chiral Alkenes via Triplet Energy Transfer
AU - Kratz, Thilo
AU - Steinbach, Pit
AU - Breitenlechner, Stefan
AU - Storch, Golo
AU - Bannwarth, Christoph
AU - Bach, Thorsten
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/6/15
Y1 - 2022/6/15
N2 - A visible-light-mediated, enantioselective approach to axially chiral alkenes is described. Starting from a racemic mixture, a major alkene enantiomer is formed due to selective triplet energy transfer from a catalytically active chiral sensitizer. A catalyst loading of 2 mol % was sufficient to guarantee consistently high enantioselectivities and yields (16 examples, 51%-quant., 81-96% ee). NMR studies and DFT computations revealed that triplet energy transfer is more rapid within the substrate-catalyst complex of the minor alkene enantiomer. Since this enantiomer is continuously racemized, the major enantiomer is enriched in the photostationary state.
AB - A visible-light-mediated, enantioselective approach to axially chiral alkenes is described. Starting from a racemic mixture, a major alkene enantiomer is formed due to selective triplet energy transfer from a catalytically active chiral sensitizer. A catalyst loading of 2 mol % was sufficient to guarantee consistently high enantioselectivities and yields (16 examples, 51%-quant., 81-96% ee). NMR studies and DFT computations revealed that triplet energy transfer is more rapid within the substrate-catalyst complex of the minor alkene enantiomer. Since this enantiomer is continuously racemized, the major enantiomer is enriched in the photostationary state.
UR - http://www.scopus.com/inward/record.url?scp=85132453873&partnerID=8YFLogxK
U2 - 10.1021/jacs.2c02511
DO - 10.1021/jacs.2c02511
M3 - Article
C2 - 35658423
AN - SCOPUS:85132453873
SN - 0002-7863
VL - 144
SP - 10133
EP - 10138
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 23
ER -