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Novel Pincer Complex-Catalyzed Transformations: Including Asymmetric Catalysis
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
2009 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Stockholm: Institutionen för organisk kemi , 2009. , s. 136
Nyckelord [en]
pincer, palladium, catalysis, chiral, asymmetric, palladium IV, allylation, aldol, aminoacid, C-H functionalization, cross-coupling, homoallylic, heck reaction, tridentate ligand
Nationell ämneskategori
Kemi
Forskningsämne
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-8524ISBN: 978-91-7155-825-1 (tryckt)OAI: oai:DiVA.org:su-8524DiVA: diva2:200433
Disputation
2009-03-20, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Tillgänglig från: 2009-02-26 Skapad: 2009-02-17 Senast uppdaterad: 2009-05-25Bibliografiskt granskad
Delarbeten
1. Palladium Pincer Complex Catalyzed Cross-Coupling of Vinyl Epoxides and Aziridines with Organoboronic Acids
Öppna denna publikation i ny flik eller fönster >>Palladium Pincer Complex Catalyzed Cross-Coupling of Vinyl Epoxides and Aziridines with Organoboronic Acids
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2005 Ingår i: Chemistry - A European Journal, ISSN 0947-6539, Vol. 11, nr 18, s. 5260-5268Artikel i tidskrift (Refereegranskat) Published
Identifikatorer
urn:nbn:se:su:diva-25749 (URN)
Anmärkning
Part of urn:nbn:se:su:diva-8524Tillgänglig från: 2009-02-26 Skapad: 2009-02-17Bibliografiskt granskad
2. Strategies for fine-tuning the catalytic activity of pincer-complexes
Öppna denna publikation i ny flik eller fönster >>Strategies for fine-tuning the catalytic activity of pincer-complexes
2006 (Engelska)Ingår i: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 47, nr 50, s. 8999-9001Artikel i tidskrift (Refereegranskat) 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.

Nyckelord
Pincer-complexes; Catalysis; Substituent effects; Palladium; Boron; Epoxide
Identifikatorer
urn:nbn:se:su:diva-25750 (URN)10.1016/j.tetlet.2006.08.141 (DOI)
Anmärkning
Part of urn:nbn:se:su:diva-8524Tillgänglig från: 2009-02-26 Skapad: 2009-02-17 Senast uppdaterad: 2017-12-13Bibliografiskt granskad
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
Öppna denna publikation i ny flik eller fönster >>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 (Engelska)Ingår i: The Journal of Organic Chemistry, ISSN 0022-3263, Vol. 72, nr 13, s. 4689-4697Artikel i tidskrift (Refereegranskat) Published
Identifikatorer
urn:nbn:se:su:diva-25751 (URN)10.1021/jo070288b (DOI)000247246100011 ()
Anmärkning
Part of urn:nbn:se:su:diva-8524Tillgänglig från: 2009-02-26 Skapad: 2009-02-17 Senast uppdaterad: 2009-05-25Bibliografiskt granskad
4. Palladium pincer complex-catalyzed condensation of sulfonimines and isocyanoacetate to imidazoline derivatives. Dependence of the stereoselectivity on the ligand effects
Öppna denna publikation i ny flik eller fönster >>Palladium pincer complex-catalyzed condensation of sulfonimines and isocyanoacetate to imidazoline derivatives. Dependence of the stereoselectivity on the ligand effects
2007 (Engelska)Ingår i: Advanced Synthesis & Catalysis, ISSN 1615-4150, Vol. 349, nr 17-18, s. 2585-2594Artikel i tidskrift (Refereegranskat) Published
Identifikatorer
urn:nbn:se:su:diva-10493 (URN)10.1002/adsc.200700242 (DOI)000251737500008 ()
Anmärkning
Part of urn:nbn:se:su:diva-8524Tillgänglig från: 2008-12-12 Skapad: 2008-12-12 Senast uppdaterad: 2009-05-25Bibliografiskt granskad
5. Chiral palladium-pincer complex catalyzed asymmetric condensation of sulfonimines and isocyanoacetate
Öppna denna publikation i ny flik eller fönster >>Chiral palladium-pincer complex catalyzed asymmetric condensation of sulfonimines and isocyanoacetate
2008 (Engelska)Ingår i: Tetrahedron: Asymmetry, ISSN 0957-4166, Vol. 19, nr 15, s. 1867-1870Artikel i tidskrift (Refereegranskat) Published
Identifikatorer
urn:nbn:se:su:diva-25753 (URN)10.1016/j.tetasy.2008.07.027 (DOI)000259623600019 ()
Anmärkning
Part of urn:nbn:se:su:diva-8524Tillgänglig från: 2009-02-26 Skapad: 2009-02-17 Senast uppdaterad: 2009-05-25Bibliografiskt granskad
6. Palladium-pincer complex catalyzed C-C coupling of allyl nitriles with tosyl imines via regioselective allylic C-H bond functionalization
Öppna denna publikation i ny flik eller fönster >>Palladium-pincer complex catalyzed C-C coupling of allyl nitriles with tosyl imines via regioselective allylic C-H bond functionalization
2008 (Engelska)Ingår i: Organic Letters, ISSN 1523-7060, Vol. 10, nr 13, s. 2881-2884Artikel i tidskrift (Refereegranskat) 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.

Nyckelord
allylic, c-h, bond activation, palladium, pincer, nitriles, cyanide
Nationell ämneskategori
Annan medicinsk grundvetenskap
Identifikatorer
urn:nbn:se:su:diva-14092 (URN)10.1021/ol801070n (DOI)000257211400067 ()
Anmärkning
Part of urn:nbn:se:su:diva-8524Tillgänglig från: 2009-01-26 Skapad: 2009-01-26 Senast uppdaterad: 2018-01-13Bibliografiskt granskad
7. Stereoselective pincer-complex catalyzed C-H functionalization of benzyl nitriles under mild conditions. An efficient route to β-aminonitriles
Öppna denna publikation i ny flik eller fönster >>Stereoselective pincer-complex catalyzed C-H functionalization of benzyl nitriles under mild conditions. An efficient route to β-aminonitriles
2008 (Engelska)Ingår i: Organic Letters, ISSN 1523-7060, Vol. 10, nr 22, s. 5175-5178Artikel i tidskrift (Refereegranskat) Published
Identifikatorer
urn:nbn:se:su:diva-17551 (URN)10.1021/ol8021512 (DOI)000260922500020 ()
Anmärkning
Part of urn:nbn:se:su:diva-8524Tillgänglig från: 2009-01-16 Skapad: 2009-01-16 Senast uppdaterad: 2009-05-25Bibliografiskt granskad
8. Pincer Complex-Catalyzed Coupling Reactions via Palladium (IV) Intermediates
Öppna denna publikation i ny flik eller fönster >>Pincer Complex-Catalyzed Coupling Reactions via Palladium (IV) Intermediates
2009 (Engelska)Ingår i: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 11, nr 13, s. 2852-2854Artikel i tidskrift (Refereegranskat) 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.

Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:su:diva-25756 (URN)10.1021/ol9010739 (DOI)
Anmärkning
Part of urn:nbn:se:su:diva-8524Tillgänglig från: 2009-02-26 Skapad: 2009-02-17 Senast uppdaterad: 2017-12-13Bibliografiskt granskad

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