Enantioselective hydrosilylation of prochiral ketones catalyzed by chiral BINAP-copper(I) complexes

Issenhuth, Jean‐Thomas; Dagorne, Samuel; Bellemin‐Laponnaz, Stéphane

doi:10.1016/j.crci.2009.11.002

Cited by 13 publications

(1 citation statement)

References 38 publications

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“…Enantiomerically pure γ-hydroxy acid derivatives are important synthetic building blocks which can be easily transformed into a series of natural, pharmaceutical, and agrochemical compounds . Currently, a number of methods are available for the synthesis of enantiomerically enriched γ-hydroxy acid derivatives via enzymatic reduction, kinetic resolution, asymmetric hydrosilylation, hydroboration, and other methods . However, these synthetic routes suffered from either low efficiency or poor enantioselectivity.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Ruthenium(II)/Xyl-SunPhos/Daipen-Catalyzed Hydrogenation of γ-Ketoamides

Zhao

et al. 2014

J. Org. Chem.

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Section: Introductionmentioning

confidence: 99%

Enantioselective Ruthenium(II)/Xyl-SunPhos/Daipen-Catalyzed Hydrogenation of γ-Ketoamides

Zhao

et al. 2014

J. Org. Chem.

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Asymmetric Hydrosilylation of Ketones Catalyzed by Zinc Acetate with Hindered Pybox Ligands

2014

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A highly efficient asymmetric hydrosilylation (AHS) of a wide variety of prochiral aryl ketones catalyzed by zinc acetate with TPS-he-pybox (tert-butyldiphenylsilyl hydroxyethyl pybox) ligand has been successfully developed. Cheap and readily available chiral Lewis acids based on zinc salts have been used as promising catalyst for the reduction of aryl ketones under mild conditions at room temperature leading to chiral alcohols in excellent yields and good to high enantioselectivities (up to 85% ee).Keywords: asymmetric synthesis; chiral alcohols; metal complexes; reduction; zinc Asymmetric hydrosilylation (AHS) of prochiral ketones represents one of the most efficient methods for the preparation of chiral secondary alcohols. Although the asymmetric hydrosilylation using catalysts based on expensive precious metals such as ruthenium, rhodium or iridium is well established, [1] an efficient means to access chiral alcohols by using cheaper and more environmentally friendly metals still remains a significant challenge. Noteworthy recent contributions in this field have emerged by utilizing chiral iron [2] and copper [3] complexes. Despite some advances, the demand for less expensive, environmentally more benign zinc-based catalytic systems for the asymmetric hydrosilylation of ketones is still an urgent need and of great significance because of the broad availability and biomimetic nature of zinc. Surprisingly, only few studies have been presented in this field, mostly utilizing zinc catalysts made of unstable and hazardous dialkylzinc compounds.[4] Synthesis and application of these organometallic species is dangerous and inconvenient, especially for industrial or large-scale use. Therefore, considerable efforts should be directed towards the development of cheap, reliable and safe zinc complexes for asymmetric hydrosilylation.For the first time an inorganic zinc salt was applied for asymmetric hydrosilylation by Nishiyama et al. in 2009.[5] These authors demonstrated that ketones can undergo reduction in an asymmetric manner with ees ranging at about 80% (one example with 92% ee) by using zinc acetate complexes with a ligand based on chiral diaminocyclohexane (DACH). Recently Lai [6] applied a similar zinc-based catalyst with chiral DACH ligands containing furan rings.In 2012 Beller and co-workers [7] used chiral i-Pr-(1) and Ph-pybox (2) ligands (Scheme 1) with either zinc acetate or diethylzinc. These authors showed that both of these catalysts can induce stereoselectivity in the reduction of acetophenone, but the reactions catalyzed by ZnA C H T U N G T R E N N U N G (OAc) 2 -pybox led to poor ees and converScheme 1. Structures of pybox-type ligands used in this work: i-Pr-pybox, Ph-pybox and he-pyboxes.

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Asymmetric Hydrosilylation of Aromatic Ketones Catalyzed by an Economical and Effective Copper‐Diphosphine Catalytic System in Air

Liang

Liu

2015

Chin. J. Chem.

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In the presence of the inexpensive and non‐toxic polymethylhydrosiloxane, the combination of copper(II) acetate and a chiral diphosphine displayed high catalytic efficiency in the asymmetric hydrosilylation of a series of aromatic ketones in air atmosphere and at room temperature. (R)‐1‐Arylethanols were obtained with up to 99% yield and 93% enantiomeric excess. Meanwhile, the electron effect and steric hindrance of substituents on the aromatic ring had an interesting influence on both the yields and enantioselectivities. Furthermore, a possible mechanism was presented to explain the influence of some key factors on the reaction.

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Enantioselective hydrosilylation of prochiral ketones catalyzed by chiral BINAP-copper(I) complexes

Cited by 13 publications

References 38 publications

Enantioselective Ruthenium(II)/Xyl-SunPhos/Daipen-Catalyzed Hydrogenation of γ-Ketoamides

Enantioselective Ruthenium(II)/Xyl-SunPhos/Daipen-Catalyzed Hydrogenation of γ-Ketoamides

Asymmetric Hydrosilylation of Ketones Catalyzed by Zinc Acetate with Hindered Pybox Ligands

Asymmetric Hydrosilylation of Aromatic Ketones Catalyzed by an Economical and Effective Copper‐Diphosphine Catalytic System in Air

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