Nickel-Catalyzed Regiodivergent Asymmetric Cycloadditions of α,β-Unsaturated Carbonyl Compounds

Cao, Shi; Ye, Ziqi; Chen, Yuehua; Lin, Yumei; Fang, Jia-Hua; Wang, Yuejiao; Yang, Boxuan; Gong, Lei

doi:10.31635/ccschem.021.202101465

Cited by 20 publications

(6 citation statements)

References 65 publications

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“…On the basis of these experiments and our previous experience, [42][43][44][45] a plausible reaction mechanism is proposed and is shown in Scheme 4a. The photocatalyst (PC1) is first excited to a triplet state (PC1*) by irradiation.…”

Section: Mechanism Proposalmentioning

confidence: 67%

Chiral polycyclic benzosultams from photocatalytic diastereo- and enantioselective benzylic C–H functionalization

et al. 2022

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Section: Mechanism Proposalmentioning

confidence: 67%

Chiral polycyclic benzosultams from photocatalytic diastereo- and enantioselective benzylic C–H functionalization

et al. 2022

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“…The engagement of high‐energy alkyl radical intermediates, in combination with difficulty of achieving compatible photocatalytic and asymmetric induction processes, makes the stereocontrolled C—H transformations significantly challenging. [ 66‐69 ]…”

Section: Asymmetric Transformations Of Alkanes or Cycloalkanes With P...mentioning

confidence: 99%

Recent Advances in Asymmetric Transformations of Unactivated Alkanes and Cycloalkanes through Direct C—H Functionalization

Cheng

et al. 2022

Chin. J. Chem.

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The direct conversion of unactivated alkanes and cycloalkanes into structurally diverse molecules through aliphatic C-H functionalization is a useful process, which has attracted intense interest from academia and industry. Methods to control chemo-and site-selectivity, combined with asymmetric catalysis, provide appealing access to high value-added enantiomer-enriched compounds but are far less developed. This review focuses on recent progress in (i) asymmetric reactions of alkanes or cycloalkanes with prochiral substrates which generate a stereocenter adjacent to the cleaved C(sp 3 )-H bond, and (ii) C(sp 3 )-H enantiodiscriminatory reactions creating a new stereogenic center on the carbon of a cleaved C(sp 3 )-H bond. Elegant strategies are discussed, including (a) metal carbene-induced C-H insertions by chiral rhodium catalysts, (b) metal-oxo-mediated C-H oxidation by biomimetic manganese catalysts, (c) enzyme catalysis by cytochromes P450 variants, and (d) dual catalysis by a photocatalyst and a chiral Lewis acid (CLA) or a chiral phosphoric acid (CPA). These catalytic systems can not only precisely recognize primary, secondary and tertiary C-H bonds at specific positions in alkanes and cycloalkanes, but also support a high level of stereoselectivity in the reactions. It is expected that the advances will stimulate further progress in asymmetric catalysis, synthetic methodology, pharmaceutical development and industrial processes.

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“…They demonstrated that iridium complexes with a potential hydrogen-binding site at a pyrazole ligand allowed to steer enantioselective reactions. 13 Chiral Lewis acids 14 and chiral nickel catalysts 15 have also been successfully developed for regiodiverse asymmetric [2 + 2] photocycloadditions on the formation of photoactive intermediates by the coordination of carbonyl substrates rather than hydrogen-bonding interactions. Geometrical control of pre-existing alkenes is a multifaceted challenge in contemporary organic synthesis for a long time.…”

Section: ■ Introductionmentioning

confidence: 99%

Photoexcited Chiral Copper Complex-Mediated Alkene E → Z Isomerization Enables Kinetic Resolution

et al. 2022

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While asymmetric synthesis has been established as a powerful synthetic tool for the construction of versatile enantioenriched molecules in the most efficient and practical manner, the resolution of racemates is still the most universal industrial approach to the synthesis of chiral compounds. However, the direct formation of enantiopure Z-isomers through the catalytic nonenzymatic kinetic resolution of racemic E-alkenes remains challenging. Herein, we disclose an unprecedented enantioselective E → Z isomerization mediated by a photoexcited chiral copper complex. This catalytic system enables kinetic resolution of 2-styrylpyrrolidines. This process is difficult to realize under thermal conditions. Mechanistic experiments and density functional theory (DFT) calculations revealed that different overall sensitization rates of the substrate–catalyst complex of the two enantiomers led to the observed excellent kinetic resolution efficiency. This photochemical transformation expands the potential of kinetic resolution beyond their established ground-state reactivity, furnishing a novel reaction mode for enantioselective catalysis at its excited state.

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Nickel-Catalyzed Regiodivergent Asymmetric Cycloadditions of α,β-Unsaturated Carbonyl Compounds

Cited by 20 publications

References 65 publications

Chiral polycyclic benzosultams from photocatalytic diastereo- and enantioselective benzylic C–H functionalization

Chiral polycyclic benzosultams from photocatalytic diastereo- and enantioselective benzylic C–H functionalization

Recent Advances in Asymmetric Transformations of Unactivated Alkanes and Cycloalkanes through Direct C—H Functionalization

Photoexcited Chiral Copper Complex-Mediated Alkene E → Z Isomerization Enables Kinetic Resolution

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