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Palladium-pincer complex catalyzed C-C coupling of allyl nitriles with tosyl imines via regioselective allylic C-H bond functionalization
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2008 (English)In: Organic Letters, ISSN 1523-7060, Vol. 10, no 13, 2881-2884 p.Article in journal (Refereed) Published
Abstract [en]

A mechanistically new palladium-pincer complex catalyzed allylation of sulfonimines is presented. This reaction involves C-H bond functionalization of allyl nitriles under mild conditions. The reaction proceeds with a high regioselectivity, without allyl rearrangement of the product. Modeling studies indicate that the carbon-carbon bond formation process proceeds via (η1-allyl)palladium pincer complex intermediates.

Place, publisher, year, edition, pages
2008. Vol. 10, no 13, 2881-2884 p.
Keyword [en]
allylic, c-h, bond activation, palladium, pincer, nitriles, cyanide
National Category
Other Basic Medicine
URN: urn:nbn:se:su:diva-14092DOI: 10.1021/ol801070nISI: 000257211400067OAI: diva2:180612
Part of urn:nbn:se:su:diva-8524Available from: 2009-01-26 Created: 2009-01-26 Last updated: 2009-05-25Bibliographically approved
In thesis
1. Novel Pincer Complex-Catalyzed Transformations: Including Asymmetric Catalysis
Open this publication in new window or tab >>Novel Pincer Complex-Catalyzed Transformations: Including Asymmetric Catalysis
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is focused on the development of new pincer complex-catalyzed transformations. Optimization of the catalytic properties (fine-tuning) was directed to increase the catalytic activity as well as the chemo-, stereo- and enantioselectivity of the complexes. This was achieved by varying the heteroatoms in the terdentate pincer ligand, by changing the electronic properties of the coordinated aryl moiety and by implementing chiral functionalities in the pincer complexes.

In the cross-coupling reaction of vinyl epoxides and aziridines with organoboronic acids the chemoselectivity of the reaction could be increased by employment of pincer complexes instead of commonly used Pd(0) catalysts. Furthermore, the introduction of a methoxy substituent in the aromatic subunit of the complex considerably increased the activity of the pincer complex catalyst.

Fine-tuning of the enantioselectivity in electrophilic allylation reactions was achieved by using a wide variety of new BINOL- and biphenanthrol-based pincer complexes. The highest enantioselectivity (85% ee) was obtained by applying biphenanthrol-based pincer complexes.

Stereoselective pincer complex-catalyzed condensation of sulfonylimines with isocyanoacetate could be achieved under mild reaction conditions. By application of chiral PCP catalysts, 2-imidazolines could be obtained with up to 86% ee.

A new pincer complex-catalyzed C-H bond functionalization based reaction between organonitriles and sulfonylimines affords homoallylic amines and beta-aminonitriles in high yields. The asymmetric version of this process affords beta-aminonitriles with up to 71% ee.

In the last chapter, a pincer complex-catalyzed redox coupling reaction is described. In this highly regio- and stereoselective process the integrity of the pincer catalysts is fully retained. This catalytic reaction proceeds with a high level of functional group tolerance, as allylic acetate and aryl halide functionalities are retained.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2009. 136 p.
pincer, palladium, catalysis, chiral, asymmetric, palladium IV, allylation, aldol, aminoacid, C-H functionalization, cross-coupling, homoallylic, heck reaction, tridentate ligand
National Category
Chemical Sciences
Research subject
Organic Chemistry
urn:nbn:se:su:diva-8524 (URN)978-91-7155-825-1 (ISBN)
Public defence
2009-03-20, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (English)
Available from: 2009-02-26 Created: 2009-02-17 Last updated: 2009-05-25Bibliographically approved

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Aydin, Juhanes
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Department of Organic Chemistry
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