- Kinetic Resolution of Neopentylic Secondary Alcohols by Cu-H-Catalyzed Enantioselective Silylation with Hydrosilanes
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A nonenzymatic kinetic resolution of sterically congested alcohols having a quaternary carbon atom in the β-position is reported. The catalyst system CuCl/NaOtBu/(R,R)-Ph-BPE together with a 3,5-xylyl-substituted tertiary hydrosilane enable enantioselective silylation of the hydroxy group. Several alcohols are obtained with good to excellent selectivity factors, and there are no other known straightforward methods to access these motifs.
- Oestreich, Martin,Papadopulu, Zaneta
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supporting information
p. 438 - 441
(2021/01/13)
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- Enantioselective borohydride reduction of aliphatic ketones catalyzed by ketoiminatocobalt(iii) complex with 1-chlorovinyl axial ligand
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For the enantioselective borohydride reduction of aliphatic ketones, the optically active ketoiminatocobalt(II) catalysts was successfully designed based on their axial ligand. Instead of chloroform for the aryl ketone reduction, various axial ligand precursors were examined for the aliphatic ketone. Consequently, 1, 1, 1-trichloroethane was found to be the most effective activator of the cobalt(II) complexes to generate the corresponding 1-chlorovinyl cobalt(III) derivatives as the reactive intermediate. Several aliphatic ketones were successfully reduced to afford the corresponding secondary alcohols with high enantioselectivities.
- Tsubo, Tatsuyuki,Chen, Hsiu-Hui,Yokomori, Minako,Fukui, Kosuke,Kikuchi, Satoshi,Yamada, Tohru
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supporting information; experimental part
p. 780 - 782
(2012/09/22)
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