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Opposite Enantiomers from Minor Enantiomer Recycling and Dynamic Kinetic Resolution Using a Single Biocatalyst
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0002-1743-7650
2011 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 20-21, 3980-3984 p.Article in journal (Refereed) Published
Abstract [en]

A one-pot recycling procedure comprising Lewis acid catalyzed enantioselective addition of acetyl cyanide to (E)-2-butenal to give the O-acetylated cyanohydrin and enzyme-catalyzed conversion of the minor product enantiomer back to (E)-2-butenal provided essentially enantiopure (2R,3E)-2-acetoxy-3-pentenenitrile in close to quantitative yield. The opposite enantiomer was obtained, albeit in lower yield and with lower enantiomeric purity than that observed from the minor enantiomer recycling, by dynamic kinetic resolution consisting of reversible addition of HCN to the aldehyde coupled to enzyme-catalyzed acetylation of the cyanohydrin.

Place, publisher, year, edition, pages
2011. no 20-21, 3980-3984 p.
Keyword [en]
Aldehydes, Cyanoacetylation, Enzyme catalysis, Lewis acids, Titanium
National Category
Organic Chemistry
URN: urn:nbn:se:kth:diva-40679DOI: 10.1002/ejoc.201100467ISI: 000293440900047ScopusID: 2-s2.0-79960329627OAI: diva2:443083
Swedish Research CouncilKnut and Alice Wallenberg Foundation
QC 20110923Available from: 2011-09-23 Created: 2011-09-20 Last updated: 2014-12-02Bibliographically approved
In thesis
1. Development and Studies of the Processes Involved in Minor Enantiomer Recycling
Open this publication in new window or tab >>Development and Studies of the Processes Involved in Minor Enantiomer Recycling
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes the development and rationalization of processes involved in a new methodology developed in our group, minor enantiomer recycling.

The first part of the thesis addresses mechanistic studies of one of the reactions involved in minor enantiomer recycling, dual Lewis acid-Lewis base catalyzed acetylcyanation of aldehydes. The methodology uses a combination of a chiral titanium-salen  complex with a tertiary amine as a catalytic  system  in  the enantioselective  synthesis  of  O-acylated  cyanohydrins from aldehydes and ketonitriles. Mechanistic investigations revealed that the rate-determining step in the reaction changes, depending on the nature of the aldehyde that was used. It was also concluded that cyanohydrin is coordinated to the Lewis acid in the acylation step.

The second part of the thesis deals with minor enantiomer recycling, a highly selective one-pot recycling system. In a first step the product is formed as a minor and a major enantiomer by asymmetric catalysis. Recycling of the minor enantiomer, by selective kinetic resolution, regenerates the starting material. Continuous addition of a second reagent, also involved in a coupled exergonic process, leads to an increase of both yield and enantiomeric excess. Recycling procedures for the synthesis of O-acylated and O-formylated cyanohydrins have been developed with high yield and high enantiomeric excess of the products. The study includes development of the systems, comparison to other methodologies in asymmetric catalysis, and attempts to understand the processes involved.


Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. 66 p.
TRITA-CHE-Report, ISSN 1654-1081 ; 2014:53
asymmetric catalysis, biocatalysis, cyanohydrins, dual activation, Lewis acid, Lewis base, minor enantiomer recycling, recycling, titanium
National Category
Organic Chemistry
Research subject
urn:nbn:se:kth:diva-156635 (URN)978-91-7595-338-0 (ISBN)
Public defence
2014-12-18, F3, Lindstedtsvägen 26, KTH, Stockholm, 13:00 (English)

QC 20141202

Available from: 2014-12-02 Created: 2014-12-01 Last updated: 2014-12-02Bibliographically approved

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