5581-76-0Relevant articles and documents
Photocatalytic Atom-Transfer Radical Addition of Activated Chlorides to Alkenes
Kostromitin, Vladislav S.,Zemtsov, Artem A.,Levin, Vitalij V.,Dilman, Alexander D.
, p. 5336 - 5340 (2021/11/03)
A protocol for performing atom transfer radical addition of activated alkyl chlorides to alkenes is described. The reaction is promoted by blue light in the presence of an organic photocatalyst (3DPA2FBN), serving to generate free radicals, and a copper c
Ligand-Controlled Regiodivergence in Nickel-Catalyzed Hydroarylation and Hydroalkenylation of Alkenyl Carboxylic Acids**
Deng, Ruohan,Engle, Keary M.,Fu, Yue,Gao, Yang,Li, Zi-Qi,Liu, Peng,Tran, Van T.
supporting information, p. 23306 - 23312 (2020/10/19)
A nickel-catalyzed regiodivergent hydroarylation and hydroalkenylation of unactivated alkenyl carboxylic acids is reported, whereby the ligand environment around the metal center dictates the regiochemical outcome. Markovnikov hydrofunctionalization products are obtained under mild ligand-free conditions, with up to 99 % yield and >20:1 selectivity. Alternatively, anti-Markovnikov products can be accessed with a novel 4,4-disubstituted Pyrox ligand in excellent yield and >20:1 selectivity. Both electronic and steric effects on the ligand contribute to the high yield and selectivity. Mechanistic studies suggest a change in the turnover-limiting and selectivity-determining step induced by the optimal ligand. DFT calculations reveal that in the anti-Markovnikov pathway, repulsion between the ligand and the alkyl group is minimized (by virtue of it being 1° versus 2°) in the rate- and regioselectivity-determining transmetalation transition state.
Site-selective catalytic deaminative alkylation of unactivated olefins
Sun, Shang-Zheng,Romano, Ciro,Martin, Ruben
supporting information, p. 16197 - 16201 (2019/10/17)
A catalytic deaminative alkylation of unactivated olefins is described. The protocol is characterized by its mild conditions, wide scope - including the use of ethylene as substrate -, and exquisite site-selectivity pattern for both a-olefins and internal olefins, thus unlocking a new catalytic platform to forge sp3-sp3 linkages, even in the context of late-stage functionalization.
