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Ruthenium-catalyzed hydrogen transfer involving amines and imines: Mechanistic studies and synthetic applications
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with ruthenium-catalyzed hydrogen transfer involving amines and imines and is divided into two parts.

In Part 1 a mechanistic study has been performed. The complexation of the imine to the catalyst and the decomplexation patterns of the formed ruthenium-amine complexes, isotope studies, and exchange studies show that the mechanism of the hydrogen transfer involving amines and imines is different from the hydrogen transfer involving alcohols and carbonyls.

In Part 2 synthetic applications of the hydrogen transfer is presented. First the rutheniumcatalyzed transfer hydrogenation of imines by 2-propanol in an unpolar solvent was investigated. The corresponding amines were isolated in good to excellent yields. Even imines bearing labile functional groups were smoothly transferred to amines with very low catalyst loadings and short reaction times employing microwave heating. Then the reverse reaction, transfer dehydrogenation of amines to imines, was investigated using either MnO2 or oxygen as terminal oxidant. Important products such as aldimines, ketimines, and non benzylic anilines were prepared in the aerobic oxidation. We also demonstrated that the aerobic oxidation is compatible with proline-mediated organocatalysis, yielding amines in high yields and ee:s. Finally the racemization of chiral amines was investigated. A cumbersome side product formation was investigated and hampered by the use of a mild hydrogen donor, giving a mild and efficient racemization process for both primary and secondary amines.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi , 2005. , 44 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-447ISBN: 91-7155-041-0 (print)OAI: oai:DiVA.org:su-447DiVA: diva2:193998
Public defence
2005-04-29, De Geersalen, Geovetenskapens hus, Svante Arrhenius väg 8 A, Stockholm, 14:00
Opponent
Supervisors
Available from: 2005-04-07 Created: 2005-04-07Bibliographically approved
List of papers
1. Mechanism of hydrogen transfer to imines from a hydroxycyclopentadienyl ruthenium hydride: Support for a stepwise mechanism
Open this publication in new window or tab >>Mechanism of hydrogen transfer to imines from a hydroxycyclopentadienyl ruthenium hydride: Support for a stepwise mechanism
2004 In: Chemical Communications, ISSN 1359-7345, no 23, 2748-2749 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23686 (URN)
Note
Part of urn:nbn:se:su:diva-447Available from: 2005-04-07 Created: 2005-04-07Bibliographically approved
2. Ruthenium-catalyzed transfer hydrogenation of imines by propan-2-ol in benzene
Open this publication in new window or tab >>Ruthenium-catalyzed transfer hydrogenation of imines by propan-2-ol in benzene
2002 In: Chemistry - A European Journal, ISSN 0947-6539, Vol. 8, no 13, 2955-2961 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23687 (URN)
Note
Part of urn:nbn:se:su:diva-447Available from: 2005-04-07 Created: 2005-04-07Bibliographically approved
3. Efficient Ruthenium-Catalyzed Transfer Hydrogenation of Functionalized Imines by Isopropanol under Controlled Microwave Heating
Open this publication in new window or tab >>Efficient Ruthenium-Catalyzed Transfer Hydrogenation of Functionalized Imines by Isopropanol under Controlled Microwave Heating
2005 (English)In: Canadian journal of chemistry (Print), ISSN 0008-4042, E-ISSN 1480-3291, Vol. 83, no 6, 909-916 p.Article in journal (Refereed) Published
Abstract [en]

Transfer hydrogenation of various functionalized imines by isopropanol catalyzed by [Ru(CO)(2)(Ph4C4CO)](2) (3) has been studied. The use of either an oil bath or controlled microwave heating in toluene led to an efficient procedure with high turnover frequencies and the product amines were obtained in high yields. An advantage with catalyst 3 over the conventional [Ru-2(CO)(4)(mu-H)(Ph4C4COHOCC4Ph4)] (1) is the absence of an initiation period, which results in a faster reaction with 3 as compared to 1.

Keyword
transfer hydrogenation, ruthenium, imines, microwave
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:su:diva-23688 (URN)10.1139/V05-103 (DOI)
Available from: 2005-04-07 Created: 2005-04-07 Last updated: 2017-12-13Bibliographically approved
4. Dehydrogenation of aromatic amines to imines via ruthenium-catalyzed hydrogen transfer
Open this publication in new window or tab >>Dehydrogenation of aromatic amines to imines via ruthenium-catalyzed hydrogen transfer
2002 In: Chemical Communications, ISSN 1359-7345, no 10, 1144 - 1145 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23689 (URN)
Note
Part of urn:nbn:se:su:diva-447Available from: 2005-04-07 Created: 2005-04-07Bibliographically approved
5. Efficient Ruthenium-Catalyzed Aerobic Oxidation of Amines Using a Biomimetic Coupled Catalytic System
Open this publication in new window or tab >>Efficient Ruthenium-Catalyzed Aerobic Oxidation of Amines Using a Biomimetic Coupled Catalytic System
2005 In: Chemistry : a European journal, ISSN 0947-6539, Vol. 11, no 8, 2327-2334 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23690 (URN)
Note
Part of urn:nbn:se:su:diva-447Available from: 2005-04-07 Created: 2005-04-07Bibliographically approved
6. Enantioselective addition of aldehydes to amines via combined catalytic biomimetic oxidation and organocatalytic C-C- bond formation
Open this publication in new window or tab >>Enantioselective addition of aldehydes to amines via combined catalytic biomimetic oxidation and organocatalytic C-C- bond formation
2005 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 46, no 23, 3965-3968 p.Article in journal (Refereed) Published
Abstract [en]

The biomimetic catalytic enantioselective addition of aldehydes to amines is reported. This was accomplished by combining biomimetic coupled catalytic aerobic oxidation of amines involving ruthenium-induced dehydrogenation and organocatalytic asymmetric Mannich reactions. The novel one-pot reactions furnished β-amino aldehyde and α-amino acid derivatives in high yields with excellent chemoselectivity and up to >99% ee.

Place, publisher, year, edition, pages
Elsevier ltd, 2005
Keyword
Biomimetic oxidation; Catalysis; Asymmetric synthesis; Ruthenium; Proline
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-23691 (URN)10.1016/j.tetlet.2005.04.047 (DOI)
Note
Part of urn:nbn:se:su:diva-447Available from: 2005-04-07 Created: 2005-04-07 Last updated: 2017-12-13Bibliographically approved
7. An efficient and mild ruthenium-catalyzed racemization of amines: application to the synthesis of enantiomerically pure amines.
Open this publication in new window or tab >>An efficient and mild ruthenium-catalyzed racemization of amines: application to the synthesis of enantiomerically pure amines.
Show others...
2002 In: Tetrahedron letters, ISSN 0040-4039, Vol. 43, no 26, 4699- p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23692 (URN)
Note
Part of urn:nbn:se:su:diva-447Available from: 2005-04-07 Created: 2005-04-07Bibliographically approved

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