67035-84-1Relevant articles and documents
Copper-Catalyzed Intermolecular Enantioselective Radical Oxidative C(sp3)?H/C(sp)?H Cross-Coupling with Rationally Designed Oxazoline-Derived N,N,P(O)-Ligands
Gu, Qiang-Shuai,Guo, Kai-Xin,Li, Zhong-Liang,Liu, Lin,Liu, Xin-Yuan,Tian, Yu,Yang, Chang-Jiang,Ye, Liu
supporting information, p. 26710 - 26717 (2021/11/18)
The intermolecular asymmetric radical oxidative C(sp3)?C(sp) cross-coupling of C(sp3)?H bonds with readily available terminal alkynes is a promising method to forge chiral C(sp3)?C(sp) bonds because of the high atom and step economy, but remains underexplored. Here, we report a copper-catalyzed asymmetric C(sp3)?C(sp) cross-coupling of (hetero)benzylic and (cyclic)allylic C?H bonds with terminal alkynes that occurs with high to excellent enantioselectivity. Critical to the success is the rational design of chiral oxazoline-derived N,N,P(O)-ligands that not only tolerate the strong oxidative conditions which are requisite for intermolecular hydrogen atom abstraction (HAA) processes but also induce the challenging enantiocontrol. Direct access to a range of synthetically useful chiral benzylic alkynes and 1,4-enynes, high site-selectivity among similar C(sp3)?H bonds, and facile synthesis of enantioenriched medicinally relevant compounds make this approach very attractive.
Oxidation of Alkylbenzenes by S2O82--CuII in Acetic Acid and Acetonitrile
Walling, Cheves,Zhao, Chengxue,El-Taliawi, Gamil M.
, p. 4910 - 4914 (2007/10/02)
Oxidation of a series of toluenes by K2S2O8 or (NH4)2S2O8 + Cu(OAc)2 in acetic acid or acetonitrile is little affected by added water or acetate and gives benzyl acetates or benzaldehydes, respectively, in good yields.Data are consistent with initial formation of aromatic radical cations, proton loss to give benzyl radicals, and oxidation to final products by CuII.Benzyl alcohols, but not acetates, are selectively oxidized, suggesting partial equilibration of radical cations, with rates of proton loss determining product distributions.Oxidation of cumene gives chiefly α-methylstyrene which is oxidized futher to 2-phenylpropanal.Products from p-ethyltoluene and p-cumene indicate that, on a statistical basis, loss of secondary and tertiary protons is more rapid than loss of primary protons, contrary to some previous reports.These systems appear promising for studying fragmentation patterns of aromatic radical cations in general.