Research output: Contribution to journal › Article › peer-review
Dynamic Nonlinear Effects in Asymmetric Catalysis. / Bryliakov, Konstantin P.
In: ACS Catalysis, Vol. 9, No. 6, 07.06.2019, p. 5418-5438.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Dynamic Nonlinear Effects in Asymmetric Catalysis
AU - Bryliakov, Konstantin P.
PY - 2019/6/7
Y1 - 2019/6/7
N2 - For three decades, "conventional" nonlinear effects in asymmetric catalysis, commonly becoming apparent as a nonproportional relationship between the enantiomeric purity of the chiral catalyst and that of the chiral reaction product, have been extensively studied from both fundamental and practical perspectives and thoroughly reviewed. In contrast, this review is focused on dynamic nonlinear effects, with the catalyst systems exhibiting variation of enantioselectivity over the reaction course, caused by catalyst-product or catalyst-substrate interactions. Namely, such phenomena as asymmetric autoinduction, asymmetric autocatalysis, and asymmetric autoamplification are considered and the corresponding catalytic reactions are surveyed. Whenever available, data on the origins of the observed nonlinearities are presented. Several kinetic schemes, illustrating the nonlinear ee variation over the reaction course, are considered. Possible implications of dynamic nonlinear effects in asymmetric catalysis in the problem of biological homochirality on Earth are discussed briefly.
AB - For three decades, "conventional" nonlinear effects in asymmetric catalysis, commonly becoming apparent as a nonproportional relationship between the enantiomeric purity of the chiral catalyst and that of the chiral reaction product, have been extensively studied from both fundamental and practical perspectives and thoroughly reviewed. In contrast, this review is focused on dynamic nonlinear effects, with the catalyst systems exhibiting variation of enantioselectivity over the reaction course, caused by catalyst-product or catalyst-substrate interactions. Namely, such phenomena as asymmetric autoinduction, asymmetric autocatalysis, and asymmetric autoamplification are considered and the corresponding catalytic reactions are surveyed. Whenever available, data on the origins of the observed nonlinearities are presented. Several kinetic schemes, illustrating the nonlinear ee variation over the reaction course, are considered. Possible implications of dynamic nonlinear effects in asymmetric catalysis in the problem of biological homochirality on Earth are discussed briefly.
KW - asymmetric amplification
KW - asymmetric catalysis
KW - autoamplification
KW - autocatalysis
KW - autoinduction
KW - dynamic
KW - nonlinear effects
KW - MIRROR-SYMMETRY-BREAKING
KW - ENANTIOMERIC EXCESS
KW - SPONTANEOUS EMERGENCE
KW - PYRIMIDYL ALKANOL
KW - ENANTIOSELECTIVE AUTOINDUCTION
KW - AUTOCATALYTIC REACTION
KW - MANNICH REACTION
KW - ALDOL REACTION
KW - SELF-REPLICATION
KW - OXIDATIVE KINETIC RESOLUTION
UR - http://www.scopus.com/inward/record.url?scp=85067201348&partnerID=8YFLogxK
U2 - 10.1021/acscatal.9b00697
DO - 10.1021/acscatal.9b00697
M3 - Article
AN - SCOPUS:85067201348
VL - 9
SP - 5418
EP - 5438
JO - ACS Catalysis
JF - ACS Catalysis
SN - 2155-5435
IS - 6
ER -
ID: 20585004