51116-72-4Relevant articles and documents
Remote Regioselective Radical C-H Functionalization of Unactivated C-H Bonds in Amides: The Synthesis of gem-Difluoroalkenes
Hu, Qu-Ping,Cheng, Jing,Wang, Ying,Shi, Jie,Wang, Bi-Qin,Hu, Ping,Zhao, Ke-Qing,Pan, Fei
supporting information, p. 4457 - 4462 (2021/05/26)
The site-selective functionalization of unactivated aliphatic amines is an attractive and challenging synthetic approach. We herein report a general strategy for the remote site-selective functionalization of unactivated C(sp3)-H bonds in amides by photogenerated amidyl radicals to form gem-difluoroalkenes with trifluoromethyl-substituted alkenes. The site selectivity is controlled by a 1,5-hydrogen atom transfer (HAT) process of the amide. This photocatalyzed transformation shows both chemo- and site-selectivity, facilitating the formation of a secondary, tertiary, or quaternary carbon center.
Primary, Secondary, and Tertiary γ-C(sp3)-H Vinylation of Amides via Organic Photoredox-Catalyzed Hydrogen Atom Transfer
Chen, Hui,Guo, Liangliang,Yu, Shouyun
supporting information, p. 6255 - 6259 (2018/10/05)
An efficient strategy for primary, secondary and tertiary aliphatic γ-C(sp3)-H vinylation of amides with alkenylboronic acids is reported. These reactions are catalyzed by visible-light organic photoredox agents. Regioselective γ-C(sp3)-H vinylation of amides is controlled by a 1,5-hydrogen atom transfer of an amidyl radical generated in situ.
A detailed mechanistic investigation into the reaction of 3-methylpentanoic acid with Meldrum's acid utilizing online NMR spectroscopy
Dunn, Anna L.,Codina, Anna,Foley, David A.,Marquez, Brian L.,Zell, Mark T.
, p. 477 - 484 (2016/05/24)
A thorough investigation into the mechanism of the reaction of 3-methylpentanoic acid and Meldrum's acid using online NMR spectroscopy is reported. This study is an expansion of a previous analysis of this chemical transformation in the synthesis of an active pharmaceutical ingredient imagabalin. The 3-methylpentanoic acid analogue reveals similar behavior under the reaction conditions. Online NMR spectroscopy and offline characterization experiments reveal new information about the mechanism, providing conclusive spectroscopic evidence for the previously hypothesized dimer anhydride intermediate species 3-methylpentanoic anhydride as a productive intermediate. The presence of an acyl chloride intermediate species, 3-methylpentanoyl chloride, is also revealed for the first time in this synthesis.