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An Efficient One-pot Procedure for the Direct Preparation of 4,5-Dihydroisoxazoles from Amides
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry. Umeå University, Sweden.
Number of Authors: 42017 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 359, no 11, p. 1990-1995Article in journal (Refereed) Published
Abstract [en]

A Mo(CO)(6) (molybdenumhexacarbonyl) catalyzed reductive functionalization of amides to afford 5-amino substituted 4,5-dihydroisoxazoles is presented. The reduction of amides generates reactive enamines, which upon the addition of hydroximinoyl chlorides and base undergoes a 1,3-dipolar cycloaddition reaction that gives access to the desired heterocyclic compounds. The transformation of amides is highly chemoselective and tolerates functional groups such as nitro, nitriles, esters, and ketones. Furthermore, a versatile scope of 4,5-dihydroisoxazoles derived from a variety of hydroximinoyl chlorides and amides is demonstrated.

Place, publisher, year, edition, pages
2017. Vol. 359, no 11, p. 1990-1995
Keywords [en]
4, 5-dihydroisoxazole, Amides, Reductive functionalization, Chemoselectivity, Enamines
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-144789DOI: 10.1002/adsc.201700154ISI: 000402839300027OAI: oai:DiVA.org:su-144789DiVA, id: diva2:1127310
Available from: 2017-07-14 Created: 2017-07-14 Last updated: 2017-09-27Bibliographically approved
In thesis
1. Development and Applications of Molybdenum-Catalyzed Chemoselective Amide Reduction
Open this publication in new window or tab >>Development and Applications of Molybdenum-Catalyzed Chemoselective Amide Reduction
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis covers the development of catalytic methodologies for the mild and chemoselective hydrosilylation of amides. The first part describes the investigation of the Mo(CO)6-catalyzed reduction of carboxamides. It was found that the reduction could be controlled by tuning the reaction temperature and either amines or aldehydes could be obtained selectively. The system showed an unprecedented chemoselectivity and the amide reduction could take place in the presence of other reducible functional groups such as ketones, aldehydes, and imines. Moreover, the transformation could be performed on a preparative scale and was further employed in the synthesis of Donepezil, a pharmaceutical drug used in the treatment of Alzheimer´s disease.

The third chapter concerns the development of the Mo(CO)6-mediated hydrosilylation protocol for the reduction of carboxamides containing acidic α-hydrogens. In this case, enamines were formed and a high level of chemoselectivity was observed. Enamines containing sensitive functional groups such as ketones, aldehydes and imines were generated. The enamines were not isolated but used in subsequent catalytic reductive functionalization of amides, which is described in the last part of the thesis (Chapters 4 – 7). The in situ formed enamines were reacted with a wide variety of electrophiles, generating heterocyclic compounds as triazolines, triazoles, 4,5-dihydroisoxazoles and pyrimidinediones. N-sulfonylformamidines as well as thioacrylamides could also be prepared with this approach. The protocols for the synthesis of triazolines, triazoles and N-sulfonylformamidines could additionally be performed on a preparative scale, showing the practicality of the methodology.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2017. p. 92
Keywords
hydrosilylation, reduction, reductive functionalization, catalysis, amides, enamines, chemoselective
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-145560 (URN)978-91-7649-911-5 (ISBN)978-91-7649-912-2 (ISBN)
Public defence
2017-11-17, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2017-10-25 Created: 2017-09-08 Last updated: 2017-10-04Bibliographically approved

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