1436411-81-2Relevant articles and documents
Conjugate reduction of α,β-unsaturated carbonyl and carboxyl compounds with poly(methylhydrosiloxane) catalyzed by a silica-supported compact phosphane-copper complex
Kawamorita, Soichiro,Yamazaki, Kenji,Ohmiya, Hirohisa,Iwai, Tomohiro,Sawamura, Masaya
, p. 3440 - 3444 (2012)
A silica-supported, cage-type, compact phosphane (Silica-SMAP) was used for the copper-catalyzed conjugate reduction of α,β-unsaturated carbonyl and carboxyl compounds with poly(methylhydrosiloxane) (PMHS). The heterogeneous catalyst system showed high activity and chemoselectivity, and was easily separable from the reaction mixture after the reaction. Furthermore, the catalyst was reusable without loss of its high catalytic activity or selectivity.
Radical dehydroxylative alkylation of tertiary alcohols by Ti catalysis
Xie, Hao,Guo, Jiandong,Wang, Yu-Quan,Wang, Ke,Guo, Peng,Su, Pei-Feng,Wang, Xiaotai,Shu, Xing-Zhong
supporting information, p. 16787 - 16794 (2020/11/09)
Deoxygenative radical C?C bond-forming reactions of alcohols are a long-standing challenge in synthetic chemistry, and the current methods rely on multistep procedures. Herein, we report a direct dehydroxylative radical alkylation reaction of tertiary alcohols. This new protocol shows the feasibility of generating tertiary carbon radicals from alcohols and offers an approach for the facile and precise construction of all-carbon quaternary centers. The reaction proceeds with a broad substrate scope of alcohols and activated alkenes. It can tolerate a wide range of electrophilic coupling partners, including allylic carboxylates, aryl and vinyl electrophiles, and primary alkyl chlorides/bromides, making the method complementary to the cross-coupling procedures. The method is highly selective for the alkylation of tertiary alcohols, leaving secondary/primary alcohols (benzyl alcohols included) and phenols intact. The synthetic utility of the method is highlighted by its 10-g-scale reaction and the late-stage modification of complex molecules. A combination of experiments and density functional theory calculations establishes a plausible mechanism implicating a tertiary carbon radical generated via Ti-catalyzed homolysis of the C?OH bond.
Visible-light-initiated manganese-catalyzed Giese addition of unactivated alkyl iodides to electron-poor olefins
Dong, Jianyang,Wang, Xiaochen,Wang, Zhen,Song, Hongjian,Liu, Yuxiu,Wang, Qingmin
supporting information, p. 11707 - 11710 (2019/10/02)
Herein, we report a mild protocol for direct visible-light-initiated Giese addition of unactivated alkyl iodides to electron-poor olefins (Michael acceptors) with catalysis by decacarbonyl dimanganese, Mn2(CO)10, an inexpensive earth-abundant-metal catalyst. This protocol is compatible with a wide array of sensitive functional groups and has a broad substrate scope with regard to both the alkyl iodide and the Michael acceptor.
