Organocatalytic Enantioselective Nucleophilic Alkynylation of Allyl Fluorides Affording Chiral Skipped Ene‐ynes

Okusu, Satoshi; Okazaki, Hiroki; Tokunaga, Etsuko; Soloshonok, Vadim A.; Shibata, Norio

doi:10.1002/ange.201601928

Cited by 9 publications

(3 citation statements)

References 63 publications

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“…During the past decades, various powerful catalytic strategies have been disclosed for the assembly of molecular complexity with corresponding readily available alkynylation reagents (Scheme 1a). [17][18][19][20] Representatively, an efficient enantioselective allylic alkynylation has been disclosed by Hamilton et al, 21 Dabrowski et al, 22 and Okusu et al 23 with corresponding metal-and organocatalysts. Additionally, the catalytic cross-coupling reaction, which involves the migratory carbene insertion process (Scheme 1b), has been extensively studied by Barluenga and Valdés 24 and Xiao et al, 25 independently.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Three-Component Propargyloxylation for Direct Assembly of Polyfunctionalized Chiral Succinate Derivatives

Liu

Zhou

et al. 2021

CCS Chem

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An enantioselective three-component propargyloxylation reaction of propargyl alcohols, pyridotriazoles, and imines has been realized by cooperative catalysis with dirhodium complex and chiral phosphoric acid under mild conditions. This is the first example of a catalytic asymmetric three-component propargyloxylation reaction, which provides practical access to chiral polyfunctionalized succinate derivatives with adjacent quaternary and tertiary stereocenters in good to high yields with excellent enantioselectivity. In addition to the alkyne motif, pyridyl, alkoxy, amino, and alkenyl species are all tolerated under the reaction conditions. Notably, the utility of the current method is demonstrated by catalytic cyclization of the product alkyne into a variety of heterocyclic structures without loss of enantiomeric purity.

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Section: Introductionmentioning

confidence: 99%

Asymmetric Three-Component Propargyloxylation for Direct Assembly of Polyfunctionalized Chiral Succinate Derivatives

Liu

Zhou

et al. 2021

CCS Chem

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“…The enantioselective alkynylation of 76 with alkynylsilanes was catalyzed by 75 to afford 83 in good yield and enantioselectivity (Scheme 23). [58] …”

Section: Cross‐coupling Reactionsmentioning

confidence: 99%

Cross‐ and Multi‐Coupling Reactions Using Monofluoroalkanes

Iwasaki

Kambe

2023

The Chemical Record

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Carbon‐fluorine bonds are stable and have demonstrated sluggishness against various chemical manipulations. However, selective transformations of C−F bonds can be achieved by developing appropriate conditions as useful synthetic methods in organic chemistry. This review focuses on C−C bond formation at monofluorinated sp3‐hybridized carbons via C−F bond cleavage, including cross‐coupling and multi‐component coupling reactions. The C−F bond cleavage mechanisms on the sp3‐hybridized carbon centers can be primarily categorized into three types: Lewis acids promoted F atom elimination to generate carbocation intermediates; nucleophilic substitution with metal or carbon nucleophiles supported by the activation of C−F bonds by coordination of Lewis acids; and the cleavage of C−F bonds via a single electron transfer. The characteristic features of alkyl fluorides, in comparison with other (pseudo)halides as promising electrophilic coupling counterparts, are also discussed.

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“… a) General illustration for the enantioselective allylic substitution using allyl fluorides b) Previous examples of niche carbanionic latent pronucleophiles in allylic substitutions [5a,c,d,6] . c) Expanding the scope of Lewis base catalyzed allylic substitutions to common stabilized C‐centered pronucleophiles.…”

Section: Introductionmentioning

confidence: 99%

Latent Pronucleophiles in Lewis Base Catalysis: Enantioselective Allylation of Silyl Enol Ethers with Allylic Fluorides

Kumar

Lange

et al. 2023

Chemistry A European J

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Lewis base catalyzed allylations of C-centered nucleophiles have been largely limited to the niche substrates with acidic CÀ H substituted for CÀ F bonds at the stabilized carbanionic carbon. Herein we report that the concept of latent pronucleophiles serves to overcome these limitations and allow for a variety of common stabilized C-nucleophiles, when they are introduced as the corresponding silylated compounds, to undergo enantioselective allylations using allylic fluorides. The reactions of silyl enol ethers afford the allylation products in good yields and with high degree of regio/stereoselectivity as well as diastereoselectivity when cyclic silyl enol ethers are used. Further examples of silylated stabilized carbon nucleophiles that undergo efficient allylation speak in favor of the general applicability of this concept to C-centered nucleophiles.

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Organocatalytic Enantioselective Nucleophilic Alkynylation of Allyl Fluorides Affording Chiral Skipped Ene‐ynes

Cited by 9 publications

References 63 publications

Asymmetric Three-Component Propargyloxylation for Direct Assembly of Polyfunctionalized Chiral Succinate Derivatives

Asymmetric Three-Component Propargyloxylation for Direct Assembly of Polyfunctionalized Chiral Succinate Derivatives

Cross‐ and Multi‐Coupling Reactions Using Monofluoroalkanes

Latent Pronucleophiles in Lewis Base Catalysis: Enantioselective Allylation of Silyl Enol Ethers with Allylic Fluorides

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