Hydrogenation, Transfer Hydrogenation and Hydrogen Transfer Reactions Catalyzed by Iridium Complexes

• Main Author: Quan, Xu
• Format: Doctoral Thesis
• Language: English
• Published: Stockholms universitet, Institutionen för organisk kemi 2015
• Subjects: Iridium catalyst; carbene; N; P - ligand; asymmetric hydrogenation; transfer hydrogenation; hydrogen transfer reaction; alkylation; olefin; ketone; amide
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-119701; http://nbn-resolving.de/urn:isbn:978-91-7649-255-0

The work described in this thesis is focused on the development of new bidentate iridium complexes and their applications in the asymmetric reduction of olefins, ketones and imines. Three new types of iridium complexes were synthesized, which included pyridine derived chiral N,P-iridium complexes, achiral NHC complexes and chiral NHC-phosphine complexes. A study of their catalytic applications demonstrated a high efficiency of the N,P-iridium complexes for asymmetric hydrogenation of olefins, with good enantioselectivity. The carbene complexes were found to be very efficient hydrogen transfer mediators capable of abstracting hydrogen from alcohols and subsequently transfer it to other unsaturated bonds. This hydrogen transferring property of the carbene complexes was used in the development of C–C and C–N bond formation reactions via the hydrogen borrowing process. The complexes displayed high catalytic reactivity using 0.5–1.0 mol% of the catalyst and mild reaction conditions. Finally chiral carbene complexes were found to be activated by hydrogen gas. Their corresponding iridium hydride species were able to reduce ketones and imines with high efficiency and enantioselectivity without any additives, base or acid. === <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Submitted. Paper 6: Manuscript.</p><p> </p>