139016-20-9Relevant articles and documents
Asymmetric hydrogenation of α-hydroxy ketones catalyzed by MsDPEN-Cp*Ir(III) complex
Ohkuma, Takeshi,Utsumi, Noriyuki,Watanabe, Masahito,Tsutsumi, Kunihiko,Arai, Noriyoshi,Murata, Kunihiko
, p. 2564 - 2567 (2007)
Asymmetric hydrogenation of a series of α-hydroxy aromatic ketones in methanol catalyzed by Cp*Ir(OTf)(MsDPEN) (MsDPEN = N-(methanesulfonyl)-1, 2-diphenylethylenediamine) affords the 1-aryl-1,2-ethanediols in up to 99% ee. The reaction can be conducted with a substrate-to-catalyst molar ratio at high as 6000 under 10 atm of H2-1-Hydroxy-2-propanone is also hydrogenated with high enantioselectivity.
Cis -Oxoruthenium complexes supported by chiral tetradentate amine (N4) ligands for hydrocarbon oxidations
Tse, Chun-Wai,Liu, Yungen,Wai-Shan Chow, Toby,Ma, Chaoqun,Yip, Wing-Ping,Chang, Xiao-Yong,Low, Kam-Hung,Huang, Jie-Sheng,Che, Chi-Ming
, p. 2803 - 2816 (2018/03/21)
We report the first examples of ruthenium complexes cis-[(N4)RuIIICl2]+ and cis-[(N4)RuII(OH2)2]2+ supported by chiral tetradentate amine ligands (N4), together with a high-valent cis-dioxo complex cis-[(N4)RuVI(O)2]2+ supported by the chiral N4 ligand mcp (mcp = N,N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)cyclohexane-1,2-diamine). The X-ray crystal structures of cis-[(mcp)RuIIICl2](ClO4) (1a), cis-[(Me2mcp)RuIIICl2]ClO4 (2a) and cis-[(pdp)RuIIICl2](ClO4) (3a) (Me2mcp = N,N′-dimethyl-N,N′-bis((6-methylpyridin-2-yl)methyl)cyclohexane-1,2-diamine, pdp = 1,1′-bis(pyridin-2-ylmethyl)-2,2′-bipyrrolidine)) show that the ligands coordinate to the ruthenium centre in a cis-α configuration. In aqueous solutions, proton-coupled electron-transfer redox couples were observed for cis-[(mcp)RuIII(O2CCF3)2]ClO4 (1b) and cis-[(pdp)RuIII(O3SCF3)2]CF3SO3 (3c′). Electrochemical analyses showed that the chemically/electrochemically generated cis-[(mcp)RuVI(O)2]2+ and cis-[(pdp)RuVI(O)2]2+ complexes are strong oxidants with E° = 1.11-1.13 V vs. SCE (at pH 1) and strong H-atom abstractors with DO-H = 90.1-90.8 kcal mol-1. The reaction of 1b or its (R,R)-mcp counterpart with excess (NH4)2[CeIV(NO3)6] (CAN) in aqueous medium afforded cis-[(mcp)RuVI(O)2](ClO4)2 (1e) or cis-[((R,R)-mcp)RuVI(O)2](ClO4)2 (1e?), respectively, a strong oxidant with E(RuVI/V) = 0.78 V (vs. Ag/AgNO3) in acetonitrile solution. Complex 1e oxidized various hydrocarbons, including cyclohexane, in acetonitrile at room temperature, affording alcohols and/or ketones in up to 66% yield. Stoichiometric oxidations of alkenes by 1e or 1e? in tBuOH/H2O (5:1 v/v) afforded diols and aldehydes in combined yields of up to 98%, with moderate enantioselectivity obtained for the reaction using 1e?. The cis-[(pdp)RuII(OH2)2]2+ (3c)-catalysed oxidation of saturated C-H bonds, including those of ethane and propane, with CAN as terminal oxidant was also demonstrated.
Chiral Ion-Pair Organocatalyst-Promoted Efficient Enantio-selective Reduction of α-Hydroxy Ketones
Zhang, Yiliang,He, Li,Shi, Lei
, p. 1926 - 1931 (2018/03/27)
The enantioselective reduction of α-hydroxy ketones with catecholborane has been developed employing 5 mol% of an 1,1′-bi-2-naphthol (BINOL)-derived ion-pair organocatalyst. This methodology provides a straightforward access to the corresponding aromatic 1,2-diols in high yields (up to 90%) with excellent enantioselectivities (up to 97%). Furthermore, the α-amino ketones also could be reduced with moderate ee values under mild reaction condition. (Figure presented.).
