23426-03-1Relevant articles and documents
Rhodium-Catalyzed meta-Selective C?H Carboxylation Reaction of 1,1-Diarylethylenes via Hydrorhodation-Rhodium Migration
Caner, Joaquim,Iwasawa, Nobuharu,Saito, Takanobu,Toriumi, Naoyuki
supporting information, p. 23349 - 23356 (2021/09/18)
A meta-selective C?H carboxylation reaction of 1,1-diarylethylene derivatives with CO2 by using a rhodium catalyst with NaOiPr as a stoichiometric reductant has been achieved. Together with hydrogenation of the ethylene moiety, a carboxyl group was introduced to the meta-position of the aryl ring with high selectivity over the ortho-positions. Experimental and computational mechanistic studies indicate that this carboxylation reaction proceeds via hydrorhodation on the ethylene moiety, followed by 1,4-rhodium migration and successive 1,2-rhodium migration on the aryl ring. The use of a bulky phosphine ligand seems to be the key to this unusual aryl-to-aryl 1,2-rhodium shift.
Visible-Light-Driven Reductive Carboarylation of Styrenes with CO2 and Aryl Halides
Gao, Yuzhen,Li, Gang,Wang, Hao,Zhou, Chunlin
supporting information, p. 8122 - 8129 (2020/05/20)
The first example of visible-light-driven reductive carboarylation of styrenes with CO2 and aryl halides in a regioselective manner has been achieved. A broad range of aryl iodides and bromides were compatible with this reaction. Moreover, pyridyl halides, alkyl halides, and even aryl chlorides were also viable with this method. These findings may stimulate the exploration of novel visible-light-driven Meerwein arylation-addition reactions with user-friendly aryl halides as the radical sources and the photocatalytic utilization of CO2
Synergistic N-Heterocyclic Carbene/Palladium-Catalyzed Umpolung 1,4-Addition of Aryl Iodides to Enals
Yang, Wenjun,Ling, Bo,Hu, Bowen,Yin, Haolin,Mao, Jianyou,Walsh, Patrick J.
supporting information, p. 161 - 166 (2019/12/03)
An umpolung 1,4-addition of aryl iodides to enals promoted by cooperative (terpy)Pd/NHC catalysis was developed that generates various bioactive β,β-diaryl propanoate derivatives. This system is not only the first reported palladium-catalyzed arylation of NHC-bound homoenolates but also expands the scope of NHC-induced umpolung transformations. A diverse array of functional groups such as esters, nitriles, alcohols, and heterocycles are tolerated under the mild conditions. This method also circumvents the use of moisture-sensitive organometallic reagents.
