104315-86-8Relevant articles and documents
Copper-Catalyzed Trifluoromethylation of Alkyl Bromides
Kornfilt, David J.P.,Macmillan, David W.C.
, p. 6853 - 6858 (2019)
Copper oxidative addition into organohalides is a challenging two-electron process. In contrast, formal oxidative addition of copper to C sp2 carbon-bromine bonds can be accomplished by employing latent silyl radicals under photoredox conditions. This novel paradigm for copper oxidative addition has now been applied to a Cu-catalyzed cross-coupling of C sp3-bromides. Specifically, a copper/photoredox dual catalytic system for the coupling of alkyl bromides with trifluoromethyl groups is presented. This operationally simple and robust protocol successfully converts a variety of alkyl, allyl, benzyl, and heterobenzyl bromides into the corresponding alkyl trifluoromethanes.
Nickel-catalyzed carbonylation of secondary trifluoromethylated, difluoromethylated, and nonfluorinated aliphatic electrophiles with arylboronic acids under 1 atm of co
Cheng, Ran,Zhao, Hai-Yang,Zhang, Shu,Zhang, Xingang
, p. 36 - 42 (2020)
The nickel-catalyzed carbonylation of aliphatic electrophiles with the most straightforward CO remains challenging. Here, we describe an example of the nickel-catalyzed carbonylation of secondary alkyl halides with arylboronic acids under 1 atm of CO. The reaction exhibits high functional group tolerance and a broad substrate scope, including trifluoromethylated, difluoromethylated, and difluoroacetylated secondary alkyl iodides and secondary benzyl bromides, providing a general and cost-efficient method to access alkyl ketones, especially α-trifluoromethylated alkyl ketones that are of great interest in medicinal chemistry. Preliminary mechanistic studies reveal that a bimetallic oxidative addition is likely involved in the reaction.
Radical-Mediated Strategies for the Functionalization of Alkenes with Diazo Compounds
Su, Yong-Liang,Liu, Geng-Xin,Liu, Jun-Wen,Tram, Linh,Qiu, Huang,Doyle, Michael P.
supporting information, p. 13846 - 13855 (2020/09/21)
One of the most common reactions of diazo compounds with alkenes is cyclopropanation, which occurs through metal carbene or free carbene intermediates. Alternative functionalization of alkenes with diazo compounds is limited, and a methodology for the addition of the elements of Z-CHR2 (with Z = H or heteroatom, and CHR2 originates from N2 CR2) across a carbon-carbon double bond has not been reported. Here we report a novel reaction of diazo compounds utilizing a radical-mediated addition strategy to achieve difunctionalization of diverse alkenes. Diazo compounds are transformed to carbon radicals with a photocatalyst or an iron catalyst through PCET processes. The carbon radical selectively adds to diverse alkenes, delivering new carbon radical species, and then forms products through hydroalkylation by thiol-assisted hydrogen atom transfer (HAT), or forms azidoalkylation products through an iron catalytic cycle. These two processes are highly complementary, proceed under mild reaction conditions, and show high functional group tolerance. Furthermore, both transformations are successfully performed on a gram-scale, and diverse γ-amino esters, γ-amino alcohols, and complex spirolactams are easily prepared with commercially available reagents. Mechanistic studies reveal the plausible pathways that link the two processes and explain the unique advantages of each.
Cobalt-Catalyzed Radical Hydrotrifluoroethylation of Styrenes with Trifluoroethyl Iodide
He, Bin,Pan, Qijun,Guo, Yong,Chen, Qing-Yun,Liu, Chao
supporting information, p. 6552 - 6556 (2020/09/02)
The cobalt-catalyzed radical trifluoroethylation of styrenes with CF3CH2I under mild conditions is described. By controlling the reaction conditions, we realized both radical trifluoroethylation self-coupling and hydrotrifluoroethylation of styrenes. The
