Palladium‐Catalyzed Regio‐, Diastereo‐, and Enantioselective 1,2‐Arylfluorination of Internal Enamides

Yang, Xi; Wang, Chenchen; Zhang, Qian; Qü, Jingping; Chen, Yifeng

doi:10.1002/anie.202012882

Cited by 40 publications

(34 citation statements)

References 97 publications

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“…The products were formed in varying yields and with excellent ees (Scheme 19). [48] All arylfluorination methods discussed above used alkenes with an electron-rich C=C bond. In contrast, Fustero, Toste, and coworkers reported enantioselective β,β-arylfluorination of electron-deficient olefins under homogeneous conditions with NFSI as oxidant/fluorine source.…”

Section: Pd-catalyzed Alkene Fluorofunctionalizationsmentioning

confidence: 99%

“…Up to date, most asymmetric olefin fluorofunctionalizations utilize organocatalysis or phase‐transfer catalysis [44] . However, there are methods using Pd catalysis [45–50] …”

Section: Asymmetric C−f Bond Forming Reactions Using Chiral Metal Complexes As Catalystsmentioning

confidence: 99%

“…[44] However, there are methods using Pd catalysis. [45][46][47][48][49][50] Pd-catalyzed CÀ F bond formation is difficult compared to other carbon-heteroatom bond formations, mainly because reductive elimination of alkyl and aryl fluorides from 16-electron Pd(II) complexes (intermediates of most Pd-catalyzed carbonheteroatom bond formations) has very high barrier. Fortunately, it was discovered in the 2000s that analogous reactions of Pd(IV) complexes have considerably lower barriers.…”

Section: Pd-catalyzed Alkene Fluorofunctionalizationsmentioning

confidence: 99%

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Asymmetric Methods for Carbon‐Fluorine Bond Formation

et al. 2021

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In memory of Ferenc FülöpAs a consequence of the ever-increasing relevance of fluorinated drugs in medicinal chemistry, organofluorine chemistry has become a hot topic research area during the last decade. Asymmetric carbon-fluorine bond-forming reactions have enormously developed in recent years with considerable findings related to novel reactions and synthetic approaches. These new synthetic efforts have contributed to the access to a growing number of fluorinated molecules and complex natural or synthetic products of high relevance in medicinal chemistry and drug research. Illustrative examples of novel synthetic methodologies, including organocatalytic processes, asymmetric syntheses or phase-transfer catalytic methods for the enantioselective incorporation of fluorine atom(s) into versatile molecular entities, are covered in the current Review, focusing on main contributions of the last ten years.

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Section: Pd-catalyzed Alkene Fluorofunctionalizationsmentioning

confidence: 99%

“…Up to date, most asymmetric olefin fluorofunctionalizations utilize organocatalysis or phase‐transfer catalysis [44] . However, there are methods using Pd catalysis [45–50] …”

Section: Asymmetric C−f Bond Forming Reactions Using Chiral Metal Complexes As Catalystsmentioning

confidence: 99%

Section: Pd-catalyzed Alkene Fluorofunctionalizationsmentioning

confidence: 99%

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Asymmetric Methods for Carbon‐Fluorine Bond Formation

et al. 2021

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“…However, the enantioselective synthesis of nonaromatic heterocyclic motifs such as pyrrolidinone via reductive difunctionalization of monosubstituted alkene has not been achieved, likely due to the difficulty in controlling the eantiodetermining step. On the basis of our continuing research interest in carbonylation 16 and enantioselective difunctionalization of alkenes, 17 we disclose a newly designed…”

Section: Scheme 2 Transition-metal-catalyzed Asymmetric Synthesis Of -Alkylated -Lactammentioning

confidence: 99%

“…However, the enantioselective synthesis of non-aromatic heterocyclic motifs such as pyrrolidinone via reductive difunctionalization of mono-substituted alkene has not been achieved, likely due to the difficulty in controlling eantiodetermining step. On the basis of our continuing research interest in carbonylation 16 and enantioselective difunctionalization of alkenes, 17 we disclose a newly designed 8quinoline imidazoline (Quinim) ligand enabled Ni-catalyzed enantioselective reductive cross-coupling of mono-substituted alkene-tethered carbamoyl chloride with unactivated primary alkyl iodide to access chiral pyrrolidinone bearing a tertiary carbon centre without any erosion of ee (Scheme 2c).…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of α-Alkylated γ-Lactam via Nickel/8-Quinim-Catalyzed Reductive Alkyl-Carbamoylation of Unactivated Alkene

Wu¹,

Shrestha²,

Chen³

2021

Synlett

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Chiral-auxiliary-mediated synthesis represents the most frequently used synthetic tool for the induction of chirality on α-position of γ-lactams in organic synthesis. However, the general strategy requires the stoichiometric use of chiral reagents with multiple manipulation steps. Transition-metal-catalyzed asymmetric alkene dicarbofunctionalization using readily available substrates under mild conditions allows the simultaneous construction of two vicinal chemical bonds and a chiral carbon center, hence, gain expedient access to chiral heterocycles. Herein, we disclose a Ni-catalyzed enantioselective reaction of 3-butenyl carbamoyl chloride and primary alkyl iodide enabled by a newly designed chiral 8-quinoline imidazoline ligand (8-Quinim). This protocol features broad functional group tolerance and high enantioselectivities, achieving unprecedented synthesis of chiral nonaromatic heterocycles via catalytic reductive protocol.1 Introduction2 Development of 8-Quinim Ligand3 Nickel/8-Quinim-Catalyzed Enantioselective Synthesis of Chiral α-Alkylated γ-Lactam4 Conclusion and Outlook

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A Sterically Tuned Directing Auxiliary Promotes Catalytic 1,2‐Carbofluorination of Alkenyl Carbonyl Compounds**

et al. 2022

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The site‐selective palladium‐catalyzed three‐component coupling of unactivated alkenyl carbonyl compounds, aryl‐ or alkenylboronic acids, and N‐fluorobenzenesulfonimide is described herein. Tuning of the steric environment on the bidentate directing auxiliary enhances regioselectivity and facilitates challenging C(sp3)−F reductive elimination from a PdIV intermediate to afford 1,2‐carbofluorination products in moderate to good yields.

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Palladium‐Catalyzed Regio‐, Diastereo‐, and Enantioselective 1,2‐Arylfluorination of Internal Enamides

Cited by 40 publications

References 97 publications

Asymmetric Methods for Carbon‐Fluorine Bond Formation

Asymmetric Methods for Carbon‐Fluorine Bond Formation

Asymmetric Synthesis of α-Alkylated γ-Lactam via Nickel/8-Quinim-Catalyzed Reductive Alkyl-Carbamoylation of Unactivated Alkene

A Sterically Tuned Directing Auxiliary Promotes Catalytic 1,2‐Carbofluorination of Alkenyl Carbonyl Compounds**

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