286415-02-9Relevant articles and documents
RETRACTED ARTICLE: The Manganese(I)-Catalyzed Asymmetric Transfer Hydrogenation of Ketones: Disclosing the Macrocylic Privilege
Passera, Alessandro,Mezzetti, Antonio
supporting information, p. 187 - 191 (2019/12/11)
The bis(carbonyl) manganese(I) complex [Mn(CO)2(1)]Br (2) with a chiral (NH)2P2 macrocyclic ligand (1) catalyzes the asymmetric transfer hydrogenation of polar double bonds with 2-propanol as the hydrogen source. Ketones (43 substrates) are reduced to alcohols in high yields (up to >99 %) and with excellent enantioselectivities (90–99 % ee). A stereochemical model based on attractive CH–π interactions is proposed.
Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H2 Activation Mode
Buhaibeh, Ruqaya,Filippov, Oleg A.,Bruneau-Voisine, Antoine,Willot, Jérémy,Duhayon, Carine,Valyaev, Dmitry A.,Lugan, No?l,Canac, Yves,Sortais, Jean-Baptiste
supporting information, p. 6727 - 6731 (2019/04/17)
Deprotonation of the MnI NHC-phosphine complex fac-[MnBr(CO)3(κ2P,C-Ph2PCH2NHC)] (2) under a H2 atmosphere readily gives the hydride fac-[MnH(CO)3(κ2P,C-Ph2PCH2NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO)3(κ3P,C,C-Ph2PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16-e mangana-substituted phosphonium ylide complex fac-[Mn(CO)3(κ2P,C-Ph2P=CHNHC)] (6 b) as key intermediate able to activate H2 via a non-classical mode of metal-ligand cooperation implying a formal λ5-P–λ3-P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre-catalysts for ketone hydrogenation in the MnI series reported to date (TON up to 6200).
Heterogeneous asymmetric hydrogenation of heteroaromatic methyl ketones catalyzed by cinchona-modified iridium catalysts
Li, Chun,Zhang, Lin,Zheng, Congye,Zheng, Xueli,Fu, Haiyan,Chen, Hua,Li, Ruixiang
, p. 821 - 824 (2014/06/23)
A heterogeneous iridium catalyst was synthesized with silica particles as support for the hydrogenation of heteroaromatic methyl ketones. The catalyst and support were characterized by solid-state NMR, HTEM, SEM, XPS, and BET. A series of heteroaromatic methyl ketones were investigated at room temperature. The catalytic system was effective and more than 99% conversion and up to 83.6% enantioselectivity were obtained in the hydrogenation of heteroaromatic methyl ketones.
