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Novel Pincer Complex-Catalyzed Transformations: Including Asymmetric Catalysis
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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.
Keyword [en]
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
Identifiers
URN: urn:nbn:se:su:diva-8524ISBN: 978-91-7155-825-1 (print)OAI: oai:DiVA.org:su-8524DiVA: diva2:200433
Public defence
2009-03-20, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2009-02-26 Created: 2009-02-17 Last updated: 2009-05-25Bibliographically approved
List of papers
1. Palladium Pincer Complex Catalyzed Cross-Coupling of Vinyl Epoxides and Aziridines with Organoboronic Acids
Open this publication in new window or tab >>Palladium Pincer Complex Catalyzed Cross-Coupling of Vinyl Epoxides and Aziridines with Organoboronic Acids
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2005 In: Chemistry - A European Journal, ISSN 0947-6539, Vol. 11, no 18, 5260-5268 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25749 (URN)
Note
Part of urn:nbn:se:su:diva-8524Available from: 2009-02-26 Created: 2009-02-17Bibliographically approved
2. Strategies for fine-tuning the catalytic activity of pincer-complexes
Open this publication in new window or tab >>Strategies for fine-tuning the catalytic activity of pincer-complexes
2006 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1873-3581, Vol. 47, no 50, 8999-9001 p.Article in journal (Refereed) Published
Abstract [en]

Various methoxy substituted pincer-complexes were prepared in order to study the substituent effects on the catalytic activity in palladium catalyzed opening of vinyl epoxides and boronation of cinnamyl alcohol. The results clearly show that methoxy substitution at the para-position of the pincer-complex leads to up to fourfold acceleration of the catalytic reactions, while substitution of the side-arms does not change the activity of the complex or leads to a slight deceleration of the catalytic processes.

Keyword
Pincer-complexes; Catalysis; Substituent effects; Palladium; Boron; Epoxide
Identifiers
urn:nbn:se:su:diva-25750 (URN)10.1016/j.tetlet.2006.08.141 (DOI)
Note
Part of urn:nbn:se:su:diva-8524Available from: 2009-02-26 Created: 2009-02-17 Last updated: 2010-05-21Bibliographically approved
3. Synthesis and Catalytic Application of Chiral 1,1‘-Bi-2-naphthol- and Biphenanthrol-Based Pincer Complexes: Selective Allylation of Sulfonimines with Allyl Stannane and Allyl Trifluoroborate
Open this publication in new window or tab >>Synthesis and Catalytic Application of Chiral 1,1‘-Bi-2-naphthol- and Biphenanthrol-Based Pincer Complexes: Selective Allylation of Sulfonimines with Allyl Stannane and Allyl Trifluoroborate
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2007 (English)In: The Journal of Organic Chemistry, ISSN 0022-3263, Vol. 72, no 13, 4689-4697 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25751 (URN)10.1021/jo070288b (DOI)000247246100011 ()
Note
Part of urn:nbn:se:su:diva-8524Available from: 2009-02-26 Created: 2009-02-17 Last updated: 2009-05-25Bibliographically approved
4. Palladium pincer complex-catalyzed condensation of sulfonimines and isocyanoacetate to imidazoline derivatives. Dependence of the stereoselectivity on the ligand effects
Open this publication in new window or tab >>Palladium pincer complex-catalyzed condensation of sulfonimines and isocyanoacetate to imidazoline derivatives. Dependence of the stereoselectivity on the ligand effects
2007 (English)In: Advanced Synthesis & Catalysis, ISSN 1615-4150, Vol. 349, no 17-18, 2585-2594 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-10493 (URN)10.1002/adsc.200700242 (DOI)000251737500008 ()
Note
Part of urn:nbn:se:su:diva-8524Available from: 2008-12-12 Created: 2008-12-12 Last updated: 2009-05-25Bibliographically approved
5. Chiral palladium-pincer complex catalyzed asymmetric condensation of sulfonimines and isocyanoacetate
Open this publication in new window or tab >>Chiral palladium-pincer complex catalyzed asymmetric condensation of sulfonimines and isocyanoacetate
2008 (English)In: Tetrahedron: Asymmetry, ISSN 0957-4166, Vol. 19, no 15, 1867-1870 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25753 (URN)10.1016/j.tetasy.2008.07.027 (DOI)000259623600019 ()
Note
Part of urn:nbn:se:su:diva-8524Available from: 2009-02-26 Created: 2009-02-17 Last updated: 2009-05-25Bibliographically approved
6. Palladium-pincer complex catalyzed C-C coupling of allyl nitriles with tosyl imines via regioselective allylic C-H bond functionalization
Open this publication in new window or tab >>Palladium-pincer complex catalyzed C-C coupling of allyl nitriles with tosyl imines via regioselective allylic C-H bond functionalization
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.

Keyword
allylic, c-h, bond activation, palladium, pincer, nitriles, cyanide
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:su:diva-14092 (URN)10.1021/ol801070n (DOI)000257211400067 ()
Note
Part of urn:nbn:se:su:diva-8524Available from: 2009-01-26 Created: 2009-01-26 Last updated: 2009-05-25Bibliographically approved
7. Stereoselective pincer-complex catalyzed C-H functionalization of benzyl nitriles under mild conditions. An efficient route to β-aminonitriles
Open this publication in new window or tab >>Stereoselective pincer-complex catalyzed C-H functionalization of benzyl nitriles under mild conditions. An efficient route to β-aminonitriles
2008 (English)In: Organic Letters, ISSN 1523-7060, Vol. 10, no 22, 5175-5178 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-17551 (URN)10.1021/ol8021512 (DOI)000260922500020 ()
Note
Part of urn:nbn:se:su:diva-8524Available from: 2009-01-16 Created: 2009-01-16 Last updated: 2009-05-25Bibliographically approved
8. Pincer Complex-Catalyzed Coupling Reactions via Palladium (IV) Intermediates
Open this publication in new window or tab >>Pincer Complex-Catalyzed Coupling Reactions via Palladium (IV) Intermediates
2009 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 11, no 13, 2852-2854 p.Article in journal (Refereed) Published
Abstract [en]

Palladium pincer complexes directly catalyze the redox coupling reactions of functionalized alkenes and iodonium salts. The catalytic process, which is suitable for mild catalytic functionalization of allylic acetates and electron-rich alkenes, probably occurs through Pd(IV) intermediates. Due to the strong metal−ligand interactions, the oxidation of phosphine and amine ligands of the pincer complexes can be avoided in the presented reactions.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-25756 (URN)10.1021/ol9010739 (DOI)
Note
Part of urn:nbn:se:su:diva-8524Available from: 2009-02-26 Created: 2009-02-17 Last updated: 2013-05-02Bibliographically approved

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