CaltechAUTHORS
  A Caltech Library Service

Caution in the Use of Nonlinear Effects as a Mechanistic Tool for Catalytic Enantioconvergent Reactions: Intrinsic Negative Nonlinear Effects in the Absence of Higher-Order Species

Kalek, Marcin and Fu, Gregory C. (2017) Caution in the Use of Nonlinear Effects as a Mechanistic Tool for Catalytic Enantioconvergent Reactions: Intrinsic Negative Nonlinear Effects in the Absence of Higher-Order Species. Journal of the American Chemical Society, 139 (11). pp. 4225-4229. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170313-071527443

[img] PDF (Mathematical analysis and experimental procedures) - Supplemental Material
See Usage Policy.

2618Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20170313-071527443

Abstract

Investigation of the dependence of product enantiometric excess (ee) on catalyst ee is a widely used tool to probe the mechanism of an enantioselective reaction; in particular, the observation of a nonlinear relationship is usually interpreted as an indication of the presence of one or more species that contain at least two units of the chiral entity. In this report, we demonstrate that catalytic enantioconvergent reactions can display an intrinsic negative nonlinear effect that originates purely from the kinetic characteristics of certain enantioconvergent processes and is independent of possible aggregation of the chiral entity. Specifically, this intrinsic negative nonlinear effect can arise when there is a kinetic resolution of the racemic starting material, and its magnitude is correlated with the selectivity factor and the conversion; the dependence on conversion provides a ready means to distinguish it from a more conventional nonlinear effect. We support our analysis with experimental data for two distinct enantioconvergent processes, one catalyzed by a chiral phosphine and the other by a chiral Pd/phosphine complex.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.7b01826DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.7b01826PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.7b01826PublisherSupporting Information
ORCID:
AuthorORCID
Kalek, Marcin0000-0002-1595-9818
Fu, Gregory C.0000-0002-0927-680X
Additional Information:© 2017 American Chemical Society. Received 21 February 2017. Published online 9 March 2017. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871), the Swedish Research Council (Grant No.: 350-2012-6645), and the Polish National Science Centre (Grant No.: 2014/15/D/ST5/02579). We thank Dr. David G. VanderVelde (NMR Facility), Dr. Scott C. Virgil (Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation), and Dr. Xu Quan for assistance. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NIHR01-GM62871
Swedish Research Council350-2012-6645
National Science Centre (Poland)2014/15/D/ST5/02579
Gordon and Betty Moore FoundationUNSPECIFIED
Issue or Number:11
Record Number:CaltechAUTHORS:20170313-071527443
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170313-071527443
Official Citation:Caution in the Use of Nonlinear Effects as a Mechanistic Tool for Catalytic Enantioconvergent Reactions: Intrinsic Negative Nonlinear Effects in the Absence of Higher-Order Species Marcin Kalek and Gregory C. Fu Journal of the American Chemical Society 2017 139 (11), 4225-4229 DOI: 10.1021/jacs.7b01826
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75045
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:13 Mar 2017 14:31
Last Modified:03 Oct 2019 16:46

Repository Staff Only: item control page