title: Expansion of the Concept of Nonlinear Effects in Catalytic Reactions Beyond Asymmetric Catalysis.
abstract: The observation and investigation of nonlinear effects in catalytic reactions provides valuable mechanistic insight. However, the applicability of this method was, until now, limited to molecules possessing chirality and therefore to asymmetric synthesis. The concept of nonlinear effects is expanded to catalytic reactions beyond asymmetric catalysis by using derivatives instead of enantiomers and by considering rates instead of enantiomeric excess. Additionally, its systematic application to investigate the mechanism of catalytic reactions is presented. By exceeding the limitation to asymmetric reactions, the study of nonlinear effects can become a general tool to elucidate reaction mechanisms.
authors.affiliation: Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-OC, Vienna, 1060, Austria.
authors.forename: Robert
authors.identifier: http://orcid.org/0000-0001-8836-6266
authors.initials: R
authors.lastname: Pollice
authors.affiliation: Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-OC, Vienna, 1060, Austria. michael.schnuerch@tuwien.ac.at.
authors.forename: Michael
authors.identifier: http://orcid.org/0000-0003-2946-9294
authors.initials: M
authors.lastname: Schnürch
keywords: cooperative effects; enantioselectivity; kinetics; reaction mechanisms; reactive intermediates