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 -