2294-71-5Relevant articles and documents
Bricout et al.
, p. 1517 (1967)
Design of Hemilabile N,N,N-Ligands in Copper-Catalyzed Enantioconvergent Radical Cross-Coupling of Benzyl/Propargyl Halides with Alkenylboronate Esters
Wang, Peng-Fei,Yu, Jiao,Guo, Kai-Xin,Jiang, Sheng-Peng,Chen, Ji-Jun,Gu, Qiang-Shuai,Liu, Ji-Ren,Hong, Xin,Li, Zhong-Liang,Liu, Xin-Yuan
, p. 6442 - 6452 (2022/04/19)
The enantioconvergent radical C(sp3)-C(sp2) cross-coupling of alkyl halides with alkenylboronate esters is an appealing tool in the assembly of synthetically valuable enantioenriched alkenes owing to the ready availability, low toxicity, and air/moisture stability of alkenylboronate esters. Here, we report a copper/chiral N,N,N-ligand catalytic system for the enantioconvergent cross-coupling of benzyl/propargyl halides with alkenylboronate esters (>80 examples) with good functional group tolerance. The key to the success is the rational design of hemilabile N,N,N-ligands by mounting steric hindrance at the ortho position of one coordinating quinoline ring. Thus, the newly designed ligand could not only promote the radical cross-coupling process in the tridentate form but also deliver enantiocontrol over highly reactive alkyl radicals in the bidentate form. Facile follow-up transformations highlight its potential utility in the synthesis of various enantioenriched building blocks as well as in the late-stage functionalization for drug discovery.
Photocatalytic Giese-Type Reaction with Alkylsilicates Bearing C,O-Bidentate Ligands
Morofuji, Tatsuya,Matsui, Yu,Ohno, Misa,Ikarashi, Gun,Kano, Naokazu
supporting information, p. 6713 - 6718 (2021/02/26)
Herein, a photocatalytic Giese-type reaction with alkylsilicates bearing C,O-bidentate ligands as stable alkyl radical precursors has been reported. The alkylsilicates were prepared in one step from organometallic reagents. Not only primary, secondary, and tertiary alkyl radicals, but also elusive methyl radicals, could be generated by using the present reaction system. The generated radicals were trapped by electron-deficient olefins bearing various functional groups to give the desired alkyl adducts. The silicon byproduct can be recovered after the photoreaction. The radical generation process was investigated by theoretical calculations, which provided an insight into the facile generation of methyl radicals from methylsilicate bearing C,O-bidentate ligands.
