50354-48-8Relevant articles and documents
Boryl Radical Activation of Benzylic C-OH Bond: Cross-Electrophile Coupling of Free Alcohols and CO2via Photoredox Catalysis
Jiang, Yi-Qian,Lan, Yu,Li, Shi-Jun,Li, Wen-Duo,Li, Yan-Lin,Wu, Yang,Xia, Ji-Bao
, (2022/04/19)
A new strategy for the direct cleavage of the C(sp3)-OH bond has been developed via activation of free alcohols with neutral diphenyl boryl radical generated from sodium tetraphenylborate under mild visible light photoredox conditions. This strategy has been verified by cross-electrophile coupling of free alcohols and carbon dioxide for the synthesis of carboxylic acids. Direct transformation of a range of primary, secondary, and tertiary benzyl alcohols to acids has been achieved. Control experiments and computational studies indicate that activation of alcohols with neutral boryl radical undergoes homolysis of the C(sp3)-OH bond, generating alkyl radicals. After reducing the alkyl radical into carbon anion under photoredox conditions, the following carboxylation with CO2 affords the coupling product.
Room Temperature Coupling of Aryldiazoacetates with Boronic Acids Enhanced by Blue Light Irradiation
da Silva, Amanda F.,Afonso, Marco A. S.,Cormanich, Rodrigo A.,Jurberg, Igor D.
, p. 5648 - 5653 (2020/04/22)
A visible-light-promoted photochemical protocol is reported for the coupling of aryldiazoacetates with boronic acids. This photochemical reaction shows great enhancement compared to the same protocol performed in the absence of light. Except for a few cases, the room temperature coupling in the dark (thermal process) generally does not work. When it does, it is likely to also involve free carbenes as key intermediates. Alternatively, photochemical reactions show a broad scope, can be performed under air and tolerate a wide variety of functional groups. Reaction-evolution monitoring, DFT calculations and control experiments have been used to evaluate the main aspects of this intricate mechanistic scenario. Biologically active molecules Adiphenine, Benactyzine and Aprophen have been prepared as examples of synthetic applications.
Nickel-Catalyzed oxidative coupling of unactivated C(sp3)-H bonds in aliphatic amides with terminal alkynes
Luo, Fei-Xian,Cao, Zhi-Chao,Zhao, Hong-Wei,Wang, Ding,Zhang, Yun-Fei,Xu, Xing,Shi, Zhang-Jie
supporting information, p. 18 - 21 (2017/04/04)
In this work, we demonstrated Ni-catalyzed oxidative coupling of unactivated C(sp3)-H bonds with terminal alkynes for construction of C(sp3)-C(sp) bonds to synthesize alkyl-substituted internal alkynes. Different amides exhibited good compatibility. Preliminary mechanistic studies were conducted to account for this alkynylation.