1565-86-2Relevant articles and documents
Chiral secondary alcohol-induced asymmetric autocatalysis: correlation between the absolute configuration of the chiral initiators and the product
Shibata, Takanori,Iwahashi, Kimiko,Kawasaki, Tsuneomi,Soai, Kenso
, p. 1759 - 1762 (2007)
In the presence of various chiral secondary alcohols as chiral initiators, an enantioselective alkylation of a pyrimidine-5-carbaldehyde using diisopropylzinc was examined: a pyrimidyl alkanol was obtained in high yield and enantiomeric excess. The correl
-
Mukaiyama,T. et al.
, p. 1455 - 1460 (1979)
-
Synthesis of β-nitro ketones from geminal bromonitroalkanes and silyl enol ethers by visible light photoredox catalysis
Cao, Haoying,Ma, Shanshan,Feng, Yanhong,Guo, Yawen,Jiao, Peng
, p. 1780 - 1783 (2022/02/17)
Various β-nitro ketones, including those bearing a β-tertiary carbon, were prepared from geminal bromonitroalkanes and trimethylsilyl enol ethers of a broad range of ketones by visible light photoredox catalysis, which were then easily converted into β-amino ketones, 1,3-amino alcohols, α,β-unsaturated ketones, β-cyano ketones and γ-nitro ketones.
Enzymatic Primary Amination of Benzylic and Allylic C(sp3)-H Bonds
Jia, Zhi-Jun,Gao, Shilong,Arnold, Frances H.
supporting information, p. 10279 - 10283 (2020/07/27)
Aliphatic primary amines are prevalent in natural products, pharmaceuticals, and functional materials. While a plethora of processes are reported for their synthesis, methods that directly install a free amine group into C(sp3)-H bonds remain unprecedented. Here, we report a set of new-to-nature enzymes that catalyze the direct primary amination of C(sp3)-H bonds with excellent chemo-, regio-, and enantioselectivity, using a readily available hydroxylamine derivative as the nitrogen source. Directed evolution of genetically encoded cytochrome P411 enzymes (P450s whose Cys axial ligand to the heme iron has been replaced with Ser) generated variants that selectively functionalize benzylic and allylic C-H bonds, affording a broad scope of enantioenriched primary amines. This biocatalytic process is efficient and selective (up to 3930 TTN and 96percent ee), and can be performed on preparative scale.
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).
