Recent advances in the metal-catalyzed asymmetric alkene hydrogenation of cyclic conjugated carbonyl compounds

Tan, Min; Peters, Bram B. C.; Andersson, Pher G.; Zhou, Taigang

doi:10.1039/d4qo00227j

Cited by 6 publications

(1 citation statement)

References 93 publications

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“…Transition metal-catalyzed asymmetric hydrogenation (AH) and asymmetric transfer hydrogenation (ATH) of ketones have been established as powerful strategies, allowing access to enantiomerically enriched alcohols, and have attracted the intensive research focus from global academic communities and have also been widely applied in the pharmaceutical industry . However, despite great progress in the past few decades, a general protocol enabling access to enantioenriched secondary alcohols with any custom combination of the α-substituents has not been realized.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Asymmetric Transfer Hydrogenation of Acylboronates: BMIDA as the Privileged Directing Group

Meng,

Lan,

Chen

et al. 2024

J. Am. Chem. Soc.

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Developing a general, highly efficient, and enantioselective catalytic method for the synthesis of chiral alcohols is still a formidable challenge. We report in this article the asymmetric transfer hydrogenation (ATH) of N-methyliminodiacetyl (MIDA) acylboronates as a general substrate-independent entry to enantioenriched secondary alcohols. ATH of acyl-MIDA-boronates with (het)aryl, alkyl, alkynyl, alkenyl, and carbonyl substituents delivers a variety of enantioenriched α-boryl alcohols. The latter are used in a range of stereospecific transformations based on the boron moiety, enabling the synthesis of carbinols with two closely related α-substituents, which cannot be obtained with high enantioselectivities using direct asymmetric hydrogenation methods, such as the (R)-cloperastine intermediate. Computational studies illustrate that the BMIDA group is a privileged enantioselectivity-directing group in Noyori−Ikariya ATH compared to the conventionally used aryl and alkynyl groups due to the favorable CH−O attractive electrostatic interaction between the η 6 -arene-CH of the catalyst and the σ-bonded oxygen atoms in BMIDA. The work expands the domain of conventional ATH and shows its huge potential in addressing challenges in symmetric synthesis.

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Section: Introductionmentioning

confidence: 99%

Catalytic Asymmetric Transfer Hydrogenation of Acylboronates: BMIDA as the Privileged Directing Group

Meng,

Lan,

Chen

et al. 2024

J. Am. Chem. Soc.

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Enantioselective Desymmetrization of 1,3‐Dicarbonyl Compounds through Transition‐Metal‐Catalyzed Intramolecular Cyclization Reactions

Liang,

Xie,

Cai

et al. 2024

ChemCatChem

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The development of reliable approaches to construct enantioenriched cyclic ketones bearing multiple stereocenters has attracted intense interest in synthetic chemistry, yet remains a challenging research area due to the difficulties in efficiently controlling the reaction enantioselectivity and diastereoselectivity. Desymmetrization of C2‐symmetric prochiral substrates has witnessed a practical and accessible strategy for creating more than one stereocenters in a single operation. In recent years, enantioselective desymmetrization of 1,3‐dicarbonyl compounds has been developed via transition‐metal‐catalyzed transformations for facile assembly of optically active cyclic ketones bearing congested stereocenters with diverse functionality. In this review, we would like to describe intramolecular enantioselective desymmetrization reactions of 1,3‐dicarbonyl derivatives, including C2‐functional group tethered 1,3‐diketones and 1,3‐diesters. This review is organized according to types of tethered groups, which aims to highlight the recent advances and briefly discuss about future perspectives in this domain.

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Asymmetric and Chemoselective Iridium Catalyzed Hydrogenation of Conjugated Unsaturated Oxime Ethers

Zhao,

Peters,

Zhang

et al. 2024

Chemistry A European J

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Research on the chemoselective metal‐catalyzed hydrogenation of conjugated p‐systems has mostly been focussed on enones. Herein, we communicate the understudied asymmetric hydrogenation of enimines catalyzed by N,P‐iridium complexes and chemoselective toward the alkene. A number of enoxime ethers underwent hydrogenation smoothly to yield the desired products in high yield and stereopurity (up to 99% yield, up to 99% ee). No hydrogenation of the C=N p‐bond was observed under the applied reaction conditions (20 bar H2, rt, DCM). It was demonstrated that the chiral oxime ether could be hydrolyzed into the ketone with complete preservation of the installed stereogenity at the α‐carbon. At last, a binding mode of the substrate to the active iridium catalyst and the consequence for the stereoselective outcome was proposed.

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Recent advances in the metal-catalyzed asymmetric alkene hydrogenation of cyclic conjugated carbonyl compounds

Abstract: The transition metal catalyzed asymmetric hydrogenation of carbon-carbon double bonds is recognized as one of the most straightforward methods for the preparation of stereopure compounds. Chiral cyclic motifs have widespread...

Cited by 6 publications

References 93 publications

Catalytic Asymmetric Transfer Hydrogenation of Acylboronates: BMIDA as the Privileged Directing Group

Catalytic Asymmetric Transfer Hydrogenation of Acylboronates: BMIDA as the Privileged Directing Group

Enantioselective Desymmetrization of 1,3‐Dicarbonyl Compounds through Transition‐Metal‐Catalyzed Intramolecular Cyclization Reactions

Asymmetric and Chemoselective Iridium Catalyzed Hydrogenation of Conjugated Unsaturated Oxime Ethers

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