Synthesis of functionalized allylic, propargylic and allenylic compounds: Selective formation of C–B, C–C, C–CF3 and C-Si bonds
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
This thesis is focused on the development of new palladium and copper- mediated reactions for functionalization of alkenes and propargylic alcohol derivatives. The synthetic utility of the 1,2-diborylated butadienes synthesized in one of these processes has also been demonstrated.
We have developed an efficient procedure for the synthesis of allenyl boronates from propargylic carbonates and acetates. This was achieved by using a bimetallic system of palladium and copper or silver as co-catalyst. The reactions were performed under mild conditions for the synthesis of a variety of allenyl boronates. Furthermore, the synthesis of 1,2-diborylated butadienes was achieved with high diastereoselectivity from propargylic epoxides. The reactivity of the 1,2-diborylated butadienes with aldehydes was studied. It was found that the initial allylboration reaction proceeds via an allenylboronate intermediate. The allenylboronate reacts readily with an additional aldehyde to construct 2-ethynylbutane-1,4-diols with moderate to high diastereoselectivity.
We have also studied the copper-mediated trifluoromethylation of propargylic halides and trifluoroacetates. It was also shown that a transfer of chirality occurred when an enantioenriched starting material was used.
In the last part of the thesis, we have described a method for palladium-catalyzed functionalization of allylic C-H bonds for the selective synthesis of allylic silanes. The protocol only works under highly oxidative conditions which suggest a mechanism involving high oxidation state palladium intermediates.
Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2015. , 73 p.
palladium catalysis, allylboration, allenylboration, trifluoromethylation, silylation, copper catalysis, borylation, bimetallic catalysis
Research subject Organic Chemistry
IdentifiersURN: urn:nbn:se:su:diva-116863ISBN: 978-91-7649-189-8OAI: oai:DiVA.org:su-116863DiVA: diva2:809077
2015-06-10, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Ito, Hajime, Professor
Szabó, Kálmán, Professor
FunderSwedish Research Council
At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 1: Accepted.2015-05-192015-04-302015-06-29Bibliographically approved
List of papers