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Mass Spectrometric Back Reaction Screening of Quasi-Enantiomeric Products as a Mechanistic Tool

Isenegger, Patrick G. and Pfaltz, Andreas. (2016) Mass Spectrometric Back Reaction Screening of Quasi-Enantiomeric Products as a Mechanistic Tool. Chemical Record, 16 (6). pp. 2534-2543.

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Official URL: http://edoc.unibas.ch/52229/

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Abstract

In this account, we discuss a mass spectrometric method that enables unambiguous identification of intermediates involved in the enantioselective step of a catalytic cycle. This method, which we originally developed for rapid evaluation of chiral catalysts, is based on monitoring the back reaction of mass-labeled quasi-enantiomeric products by ESI-MS. In this way, the intrinsic enantioselectivity of a chiral catalyst can be determined directly by quantification of catalytically relevant intermediates. By comparing the results from the forward and back reaction, direct evidence for the involvement of a catalytic intermediate in the enantioselective step can be obtained. In addition, insights about the energy profile of the catalytic cycle may be gained. The potential of back reaction screening as a mechanistic tool is demonstrated for organocatalytic aldol reactions, 1,4-additions of aldehydes to nitroolefins, Diels-Alder reactions, Michael additions, and Morita-Baylis-Hillman reactions.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Synthetische organische Chemie (Pfaltz)
UniBasel Contributors:Pfaltz, Andreas and Isenegger, Patrick
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Wiley
ISSN:1527-8999
e-ISSN:1528-0691
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:25 Jan 2017 09:03
Deposited On:25 Jan 2017 09:03

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