Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals
A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful β- and γ-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on a gram scale.
Allen, Benjamin D. W.,Hareram, Mishra Deepak,Seastram, Alex C.,McBride, Tom,Wirth, Thomas,Browne, Duncan L.,Morrill, Louis C.
p. 9241 - 9246
(2019/11/19)
Regioselective Synthesis of Carbonyl-Containing Alkyl Chlorides via Silver-Catalyzed Ring-Opening Chlorination of Cycloalkanols
A novel and regioselective approach to carbonyl-containing alkyl chlorides via silver-catalyzed ring-opening chlorination of cycloalkanols is reported. Concurrent C(sp3)-C(sp3) bond cleavage and C(sp3)-Cl bond formation efficiently occur with good yields under mild conditions, and the chlorinated products are readily transformed into other useful synthetic intermediates and drugs. The reaction features complete regioselectivity, high efficiency, and excellent practicality. (Chemical Equation Presented).
Huang, Feng-Qing,Xie, Jian,Sun, Jian-Guo,Wang, Yue-Wei,Dong, Xin,Qi, Lian-Wen,Zhang, Bo
supporting information
p. 684 - 687
(2016/03/01)
New efficient nickel-catalyzed cross-coupling reaction between two Csp3 centers
The presence of a remote unsaturation (double bond, carbonyl group, cyano group) in an alkyl halide facilitates its cross-coupling reaction with various diorganozincs in the presence of Ni(acac)2 (7.5-10 mol % in THF/NMP mixtures). These results were used to develop a new general cross-coupling reaction between functionalized diorganozincs and alkyl iodides using m- or p-trifluoromethylstyrene as a reaction promotor and Ni(acac)2 as a catalyst (7.5-10 mol %; -35 °C, 5-10 h) leading to a broad range of polyfunctional cross-coupling products.