Photoredox-catalyzed stereoselective alkylation of enamides with N-hydroxyphthalimide esters via decarboxylative cross-coupling reactions

Guo, Jingyu; Zhang, Ze-Yu; Guan, Ting; Mao, Lei-Wen; Ban, Qian; Zhao, Kai; Loh, Teck‐Peng

doi:10.1039/c9sc03070k

Cited by 77 publications

(22 citation statements)

References 108 publications

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“…12,22,24 A related class of reactions that utilize N-(acyloxy)phthalimides (or NHPI esters) involve decarboxylative alkyl additions to alkynes 25 or alkenes. [26][27][28][29][30][31][32][33][34][35][36][37] Intrigued by previous studies, we speculated if alkyl NHPI esters could be exploited in three-component processes by merging with an alkyne and an alkynyl halide to deliver synthetically valuable acyclic 1,3-enyne motifs, conjugated entities commonly embedded within natural products, pharmaceuticals, agrochemicals and materials. [38][39][40][41][42]…”

mentioning

confidence: 88%

Nickel-Catalyzed Site- and Stereoselective Reductive Alkylalkynylation of Alkynes

Jiang¹,

Pan²,

Yang³

et al. 2020

Preprint

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Development of a catalytic multicomponent reaction by orthogonal activation of readily available substrates for the streamlined difunctionalization of alkynes is a compelling objective in organic chemistry. Alkyne carboalkynylation, in particular, offers a direct entry to valuable 1,3-enynes with different substitution patterns. Here, we show that the synthesis of stereodefined 1,3-enynes featuring a trisubstituted olefin is achieved by merging alkynes, alkynyl bromides and redox-active N-(acyloxy)phthalimides through nickel-catalyzed reductive alkylalkynylation. Products are generated in up to 89% yield as single regio- and E isomers. Transformations are tolerant of diverse functional groups and the resulting 1,3-enynes are amenable to further elaboration to synthetically useful building blocks. With olefin-tethered N-(acyloxy)phthalimides, a cascade radical addition/cyclization/alkynylation process can be implemented to obtain 1,5-enynes. The present study underscores the crucial role of redox-active esters as superior alkyl group donors compared to haloalkanes in reductive alkyne dicarbofunctionalizations.

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confidence: 88%

Nickel-Catalyzed Site- and Stereoselective Reductive Alkylalkynylation of Alkynes

Jiang¹,

Pan²,

Yang³

et al. 2020

Preprint

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“…In 2019, Zhao's group [128] reported an effective method to realize the stereoselective β-C(sp 2 )-H alkylation through a photoredox decarboxylative cross-coupling reaction of enamides 45 and NHP esters 1 (Scheme 21a). In addition to high functional group tolerance, the reaction also showed high stereoselectivity, providing all E-type alkylated enamides 46.…”

Section: Scheme 17 Synthesis Of Cyclic Ketones Through Photocatalytic Cascade Cyclization Of Nhp Estersmentioning

confidence: 99%

Advances of N-Hydroxyphthalimide Esters in Photocatalytic Alkylation Reactions

He¹,

Li²,

Chen³

et al. 2021

Chinese Journal of Organic Chemistry

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N-Hydroxyphthalimide (NHP) esters are easily available, stable, inexpensive, and highly photoactive compounds, which are derived from the corresponding carboxylic acids. In recent years, the application of NHP esters in photocatalytic decarboxylative reactions has captured huge attention. Herein, the vigorous development of photocatalytic alkylation reactions using alkyl NHP esters as alkylating reagents is summarized based on the classification of photocatalysts.

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“…Most recently, several approaches involving the alkylation of tertiary enamides have been developed by Zhao, Loh and co-workers. 46 In a first paper, the authors examined the photoredox-catalyzed alkylation of tertiary enamides via a decarboxylative cross-coupling reaction. 46…”

Section: Scheme 27 Palladium-catalyzed Cross-coupling Of Two Differenmentioning

confidence: 99%

“…46 In a first paper, the authors examined the photoredox-catalyzed alkylation of tertiary enamides via a decarboxylative cross-coupling reaction. 46…”

Section: Scheme 27 Palladium-catalyzed Cross-coupling Of Two Differenmentioning

confidence: 99%

Tertiary Enamides as Versatile and Valuable Substrates to Reach Chemical Diversity

Beltran

Miesch

2020

Synthesis

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Tertiary enamides display versatile reactivity and great stability compared to their enamine congeners. This review covers progress made in the development of new methods involving the enaminic reactivity of tertiary enamides with respect to the synthesis of complex nitrogen-containing compounds. A focus on the preparation of biologically active molecules is also presented. The syntheses reported herein are classified based on their reaction type. In addition, mechanistic insights are given for most of the new transformations.1 Introduction2 [2+2] Cycloadditions3 [4+2] Cycloadditions4 Electrocyclizations and Cycloisomerizations5 Sigmatropic Rearrangements6 Nucleophilic Additions7 Tertiary Enamides as Electrophiles8 Cross-Coupling Reactions9 Tertiary-Enamide-Assisted Reactions10 Conclusion and Perspectives

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Photoredox-catalyzed stereoselective alkylation of enamides with N-hydroxyphthalimide esters via decarboxylative cross-coupling reactions

Abstract: Stereoselective β-C(sp2)–H alkylation of enamides with N-hydroxyphthalimide esters is demonstrated, affording geometrically defined alkylated enamides bearing various functional groups.

Cited by 77 publications

References 108 publications

Nickel-Catalyzed Site- and Stereoselective Reductive Alkylalkynylation of Alkynes

Nickel-Catalyzed Site- and Stereoselective Reductive Alkylalkynylation of Alkynes

Advances of N-Hydroxyphthalimide Esters in Photocatalytic Alkylation Reactions

Tertiary Enamides as Versatile and Valuable Substrates to Reach Chemical Diversity

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