Achieved by Prof. Mingchen Fu’s Research Group at Hefei University of TechnologyMuffle Furnace Applications and Reaction Processes
First Author: Zhang Tianzhen
Corresponding Author: Fu Mingchen
Title: Alcohols as Alkyl Electrophiles for Deoxygenative Heck Reaction Enabled by Excited-State Pd Catalysis
Impact Factor: 4.9
Article Link: https://pubs.acs.org/doi/full/10.1021/acs.orglett.4c03343
Research background of the paper
Alcohol compounds are abundant and cheap in nature, but the application of alcohols in traditional cross-coupling reactions is limited due to the high dissociation energy of their C-O bonds and the weak activity of hydroxyl groups as leaving groups. Based on the in-depth study of the Heck reaction, we noticed that there is no research on the use of alcohols as alkyl electrophiles for coupling reactions. Referring to the previous strategies for activating alcohols, whether the deoxygenation Heck reaction of alcohols can be achieved by pre-activating alcohols to 2-iodophenylthiocarbonate attracted our attention.
Highlights/Abstract
This paper reports the Heck reaction of alcohols as alkyl electrophiles for the first time. The authors introduce a general method for photoinduced palladium-catalyzed deoxygenation Heck reactions involving alkenyl aromatics with o-iodophenylthiocarbonate derived from alcohols. Mechanistic studies show that the deoxygenation process involves a 5-endocyclization and fragmentation process, in which free radical addition is determined to be the rate-determining step in this transformation. The one-pot process exhibits excellent selectivity for the less hindered hydroxyl groups in diols, facilitating the late functionalization of complex molecules and the scalability of gram-scale synthesis. This method highlights significant synthetic potential and can be extended to the tandem 1,1-difunctionalization of isonitriles and the intermolecular free radical tandem cyclization of N-arylacrylamides.
The LED light source used by Professor Fu Mingchen’s research group in the experiment was provided by Kemi Instrument. Anhui Kemi Instrument Co., Ltd. was also specifically mentioned in the paper. I would like to express my sincere gratitude to the professor for his choice and recognition of Ke Instruments.
