Copper-Catalyzed Asymmetric Hydrosilylation of β-Nitroethyl Aryl Ketones

Zeng, Weijun; Tan, Xuefeng; Yu, Yang; Chen, Genqiang; Zhang, Xumu

doi:10.1021/acs.orglett.9b04339

Cited by 11 publications

(6 citation statements)

References 49 publications

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“…The procedure achieved excellent yields and ee's with multiple substrates (Scheme 32). 57 The transformation was used to prepare an intermediate that had been converted to Ticagrelor, a powerful anticlotting agent (Scheme 33). When applied to the dialkyl ketone 1-nitro-4-octanone, the alcohol was obtained in 91% yield, but with only 11% ee.…”

Section: Asymmetric Reduction Of Aryl Ketonesmentioning

confidence: 99%

Organosilanes in Metal-Catalyzed, Enantioselective Reductions

Larson

Liberatore

2021

Org. Process Res. Dev.

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The growth and development of an extensive range of metals complexed with chiral ligands for the purpose of catalyzing a variety of reactions in an enantioselective manner has been impressive for its scope, chemical yields and high ee values. Chief among the classes of synthetic transformations has been that of the asymmetric reduction of prochiral substrates. These include the asymmetric reduction of prochiral ketones, imines, unsaturated aldehydes, ketones, esters, nitriles and olefins, as well as a number of asymmetric coupling reactions. In concert with these efficient catalyst systems, organosilanes have the ability to carry out any number of organic reductions under a variety of conditions. In these reactions, which in reality are hydrosilylations (hydrosilylation and reduction are considered interchangeable herein) in which the initially resulting silylated product is hydrolyzed to the ultimate desired functionality, the ability to sterically and electronically alter the organosilane reductant can contribute to the overall success of the transformation. In this review, we present a thorough compilation of the literature covering the use of organosilanes in metal-catalyzed asymmetric reductions (hydrosilylations) and coupling reactions.

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Section: Asymmetric Reduction Of Aryl Ketonesmentioning

confidence: 99%

Organosilanes in Metal-Catalyzed, Enantioselective Reductions

Larson

Liberatore

2021

Org. Process Res. Dev.

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“…Transition metal-catalyzed asymmetric hydrosilylation of ketones offers a direct and mild approach for accessing chiral alcohols with good functional group tolerance . During the past three decades, tremendous advances in the field of homogeneous catalysis have made by using the earth-abundant transition metals, such as zinc, copper, iron, , cobalt, and manganese, for asymmetric hydrosilylation of ketones. Generally, the applications of these catalytic systems were restricted to simple aryl alkyl, diaryl, and dialkyl ketones (Scheme a).…”

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confidence: 99%

Cobalt-Catalyzed Asymmetric Hydrosilylation of α-Oxygenated Ketones

et al. 2023

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An asymmetric hydrosilylation of α-oxygenated ketones was developed under the catalysis of Co(OAc) 2 in combination with a chiral phosphine-amido-oxazoline (PAO) ligand, providing a mild, efficient, and enantioselective access to a variety of synthetically useful 1,2-diol derivatives. This protocol can be carried out at the gram scale with a catalyst loading of 1 mol %, and its synthetic utility was demonstrated by efficient conversion of the optically enriched products into chiral α-hydroxy acid, 1,3dioxolan-2-one, ethylene oxide, and 1,2,3-1H-triazole.

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“…Probably this was due to the greater challenge for enantiodifferentiation of prochiral faces in these substrates. Based on our previous research on copper hydride chemistry and continued interest in copper-mediated asymmetric reductions and ligand development, we wondered whether the CuH-mediated reduction of enones could be developed to be a robust method to access structurally diverse cyclic allylic alcohols in particular (Scheme C). Herein, we report the use of DTBM-C 3 *-TunePhos as a ligand, to achieve an improved copper catalyzed asymmetric 1,2-reduction of cyclic enones and α-brominated cyclic enones, wherein excellent chemoselectivity and good to excellent enantioselectivities can be achieved.…”

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confidence: 99%

Copper-Catalyzed Enantioselective 1,2-Reduction of Cycloalkenones

et al. 2021

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We report an asymmetric 1,2-reduction of cyclic α,β-unsaturated ketones to access various enantiomerically enriched cyclic allylic alcohols under mild conditions, catalyzed by in situ generated copper hydride ligated with (R)-DTBM-C 3 *-TunePhos. α-Brominated cycloalkenones were reduced with excellent enantioselectivities of up to 98% ee, while substrates that were without αsubstituents were reduced chemoselectively, with moderate enantioselectivities.

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Copper-Catalyzed Asymmetric Hydrosilylation of β-Nitroethyl Aryl Ketones

Cited by 11 publications

References 49 publications

Organosilanes in Metal-Catalyzed, Enantioselective Reductions

Organosilanes in Metal-Catalyzed, Enantioselective Reductions

Cobalt-Catalyzed Asymmetric Hydrosilylation of α-Oxygenated Ketones

Copper-Catalyzed Enantioselective 1,2-Reduction of Cycloalkenones

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