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Iridium-catalyzed asymmetric hydrogenation of furan derivatives and thiophene 1,1-dioxides

Pauli, Larissa. Iridium-catalyzed asymmetric hydrogenation of furan derivatives and thiophene 1,1-dioxides. 2014, PhD Thesis, University of Basel, Faculty of Science.

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Official URL: http://edoc.unibas.ch/diss/DissB_11052

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Abstract

The main focus of the research presented in this dissertation was to broaden the substrate scope of the iridium-catalyzed asymmetric hydrogenation of heterocyclic compounds. In view of the fact that a widely applicable hydrogenation system for the reduction of structurally diverse furans and benzofurans is to date not available, a thorough investigation of furan, benzofuran and thiophene 1,1-dioxide derivatives was carried out. Mono- and disubstituted furan derivatives were synthesized and submitted to iridium-catalyzed hydrogenation reactions. While 3-substituted furans were reduced using a catalyst based on a cyclopentane-annulated bicyclic pyridine-phosphine ligand with high enantiomeric excess (95–99% ee) and conversion (83–99%), 2-substituted counterparts proved to be less reactive (80–97% conv., 65–82% ee) with the same catalyst. Asymmetric hydrogenation of 2,4-disubstituted furans proved to be challenging for several reasons, not least because of the problem of controlling the cis/trans selectivity. Surprisingly, in the iridium-catalyzed hydrogenation of 3-substituted benzofurans only one catalyst, based on the cyclohexane-annulated pyridine-phosphinite ligand, showed high activity and enantioselectivity (75–89% conv., 91–92% ee), whereas the five-membered ring analog suffered from moderate activity and enantioselectivity. In contrast, the 2-alkyl substituted benzofurans gave superior results (99% conv., 97–99% ee). Disubstituted thiophene 1,1-dioxides were also investigated in the iridium-catalyzed asymmetric hydrogenation. The hydrogenation of 3,4 disubstituted thiophene 1,1 dioxides using a catalyst based on a cyclopentane-annulated bicyclic pyridine-phosphine ligand gave inferior results to those obtained with their 2,5 disubstituted counterparts.
Advisors:Pfaltz, Andreas
Committee Members:Wennemers, Helma
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Synthetische organische Chemie (Pfaltz)
Item Type:Thesis
Thesis no:11052
Bibsysno:Link to catalogue
Number of Pages:163 S.
Language:English
Identification Number:
Last Modified:30 Jun 2016 10:56
Deposited On:23 Dec 2014 12:59

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