125639-56-7Relevant articles and documents
Visible-Light-Driven Catalytic Deracemization of Secondary Alcohols
Hu, Xile,Zhang, Zhikun
supporting information, p. 22833 - 22838 (2021/09/09)
Deracemization of racemic chiral compounds is an attractive approach in asymmetric synthesis, but its development has been hindered by energetic and kinetic challenges. Here we describe a catalytic deracemization method for secondary benzylic alcohols which are important synthetic intermediates and end products for many industries. Driven by visible light only, this method is based on sequential photochemical dehydrogenation followed by enantioselective thermal hydrogenation. The combination of a heterogeneous dehydrogenation photocatalyst and a chiral molecular hydrogenation catalyst is essential to ensure two distinct pathways for the forward and reverse reactions. These reactions convert a large number of racemic aryl alkyl alcohols into their enantiomerically enriched forms in good yields and enantioselectivities.
Asymmetric Magnesium-Catalyzed Hydroboration by Metal-Ligand Cooperative Catalysis
Falconnet, Alban,Magre, Marc,Maity, Bholanath,Cavallo, Luigi,Rueping, Magnus
supporting information, p. 17567 - 17571 (2019/11/13)
Asymmetric catalysis with readily available, cheap, and non-toxic alkaline earth metal catalysts represents a sustainable alternative to conventional synthesis methodologies. In this context, we describe the development of a first MgII-catalyzed enantioselective hydroboration providing the products with excellent yields and enantioselectivities. NMR spectroscopy studies and DFT calculations provide insights into the reaction mechanism and the origin of the enantioselectivity which can be explained by a metal-ligand cooperative catalysis pathway involving a non-innocent ligand.
Co6H8(PiPr3)6: A Cobalt Octahedron with Face-Capping Hydrides
Ohki, Yasuhiro,Shimizu, Yuki,Araake, Ryoichi,Tada, Mizuki,Sameera,Ito, Jun-Ichi,Nishiyama, Hisao
supporting information, p. 15821 - 15825 (2016/12/16)
A square-planar Co4amide cluster, Co4{N(SiMe3)2}4(2), and an octahedral Co6hydride cluster, Co6H8(PiPr3)6(4), were obtained from metathesis-type amide to hydride exchange reactions of a CoIIamide complex with pinacolborane (HBpin) in the absence/presence of PiPr3. The crystal structure of 4 revealed face-capping hydrides on each triangular [Co3] face, while the formal CoII2CoI4oxidation state of 4 indicated a reduction of the cobalt centers during the assembly process. Cluster 4 catalyzes the hydrosilylation of 2-cyclohexen-1-one favoring the conjugate reduction. Generation of the catalytically reactive Co cluster species was indicated by a trapping experiment with a chiral chelating agent.