Cobalt-catalyzed asymmetric hydrogenation of ketones: A remarkable additive effect on enantioselectivity

Du, Tian; Wang, Biwen; Wang, Chao; Xiao, Jianliang; Tang, Weijun

doi:10.1016/j.cclet.2020.09.011

Cited by 20 publications

(13 citation statements)

References 52 publications

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“…In line with our interests in site-selective olefin isomerization determined by kinetics via cobalt catalysis, , we commenced our studies by synthesizing a series of chiral N , N , P -pincer cobalt complexes Co-1 – Co-14 (Scheme ). These cobalt complexes show paramagnetic behavior and effective magnetic moments between 3.5 and 4.0 μ B . The crystal structures of complexes 4 and 13 showed that both complexes exhibit a distorted-trigonal-bipyramidal geometry.…”

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confidence: 99%

Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

et al. 2021

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Chiral cyclic olefins, 1-methylcyclohexenes, are versatile building blocks for the synthesis of pharmaceuticals and natural products. Despite the prevalence of these structural motifs, the development of efficient synthetic methods remains an unmet challenge. Herein we report a novel desymmetric isomerization of exocyclic olefins using a series of newly designed chiral cobalt catalysts, which enables a straightforward construction of chiral 1-methylcyclohexenes with diversified functionalities. The synthetic utility of this methodology is highlighted by a concise and enantioselective synthesis of a natural product, β-bisabolene. The versatility of the reaction products is further demonstrated by multifarious derivatizations.

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confidence: 99%

Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

et al. 2021

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“…Very recently, Tang and co-workers utilized a chiral aminophosphine fragment in the preparation of PNN-L25 via reductive amination. 125 This ligand has been applied in Co-catalyzed AH of ketones.…”

Section: Pnn-type Ligandsmentioning

confidence: 99%

“…In 2020, Farkas developed PNN-L23 and PNN-L24 and studied the relationship of the ring size of the metallacycles and the chemoselectivity while employing PNN-L23 and PNN-L24 in Ir-catalyzed hydrogenation of enones. Very recently, Tang and co-workers utilized a chiral aminophosphine fragment in the preparation of PNN-L25 via reductive amination . This ligand has been applied in Co-catalyzed AH of ketones.…”

Section: Overview Of Chiral Tridentate Ligands For Hydrogenationmentioning

confidence: 99%

Chiral Tridentate Ligands in Transition Metal-Catalyzed Asymmetric Hydrogenation

2021

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Asymmetric hydrogenation (AH) of double bonds has been one of the most effective methods for the preparation of chiral molecules and for the synthesis of important chiral building blocks. In the past 60 years, noble metals with bidentate ligands have shown marvelous reactivity and enantioselectivity in asymmetric hydrogenation of a series of prochiral substrates. In recent years, developing chiral tridentate ligands has played an increasingly important role in AH. With modular frameworks and a variety of functionalities on the side arms, chiral tridentate ligand complexes enable both reactivities and stereoselectivities. Although great achievements have been made for noble metal catalysts with chiral tridentate ligands since the 1990s, the design of chiral tridentate ligands for earth abundant metal catalysts has still been in high demand. This review summarizes the development of chiral tridentate ligands for homogeneous asymmetric hydrogenation. The philosophy of ligand design and the reaction mechanisms are highlighted and discussed as well.

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“…17 In 2020, Tang and co-workers developed a chiral Co(II)/PNN complex combined with an achiral monophosphine ligand, which slightly improved the enantioselectivities for the AH of aryl alkyl ketones. 18 Received: August 2, 2023 Published: August 16, 2023 Despite these efforts, the development of state-of-the-art chiral cobalt catalysts for the AH of ketones is still a significant challenge. Drawbacks such as unsatisfactory enantioselectivities, addition of sophisticated additives, and narrow reaction scopes still impede the application of Co-catalyzed AH of ketones in pharmaceutical and fine chemical industries.…”

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confidence: 99%

“…In 2016, Li and co-workers reported the first example of the AH of simple ketones using chiral Co(II)/PNNP complexes, affording moderate enantioselectivities for most ketone substrates (Figure a) . In 2020, Tang and co-workers developed a chiral Co(II)/PNN complex combined with an achiral monophosphine ligand, which slightly improved the enantioselectivities for the AH of aryl alkyl ketones …”

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confidence: 99%

Cobalt-Catalyzed Enantioselective Hydrogenation of Diaryl Ketones with Ferrocene-Based Secondary Phosphine Oxide Ligands

et al. 2023

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A new class of cobalt catalytic system for asymmetric hydrogenation of ketones was herein reported, involving the development of novel ferrocene-based secondary phosphine oxide ligands. An unusual P–O bidentate coordination pattern with cobalt was confirmed by an X-ray diffraction study. The bichelating tetrahedral cobalt(II) complexes afforded high reactivities (up to 99% yield) and good to excellent enantioselectivities (up to 92% ee) in the AH of various ortho-substituted diaryl ketones. In addition, the diferrocenyl cobalt complex was characterized with intriguing UV–vis absorption and electrochemical properties.

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Cobalt-catalyzed asymmetric hydrogenation of ketones: A remarkable additive effect on enantioselectivity

Cited by 20 publications

References 52 publications

Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

Chiral Tridentate Ligands in Transition Metal-Catalyzed Asymmetric Hydrogenation

Cobalt-Catalyzed Enantioselective Hydrogenation of Diaryl Ketones with Ferrocene-Based Secondary Phosphine Oxide Ligands

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