Asymmetric Sonogashira C(sp<sup>3</sup>)–C(sp) bond coupling enabled by a copper(<scp>i</scp>) complex of a new guanidine-hybrid ligand

Li, Jinzhao; Ning, Lichao; Tan, Qingfa; Feng, Xiaoming; Liu, Xiaohua

doi:10.1039/d2qo01283a

Cited by 13 publications

(5 citation statements)

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“…As illustrated in Scheme , based on the aforementioned mechanistic studies and previous reports, , we tentatively proposed a possible mechanism for this photoinduced copper-catalyzed stereoconvergent alkynylation of styrene oxide. First, the BOPA-coordinated copper(I) complex I reacted with alkynes in the presence of Cs 2 CO 3 , forming BOPA–copper(I) acetylide species II .…”

Section: Mechanistic Studiesmentioning

confidence: 54%

“…In recent years, a range of copper-catalyzed enantioselective alkynylation reactions through asymmetric radical cross-coupling have been developed . In this field, a series of anionic NNN/NNP tridentate ligands developed by Liu and our group have demonstrated its significant potential for stereoselective control. In line with our continuous studies on asymmetric alkynylation reactions, we envisioned that the regio- and stereoselective cross-coupling of racemic epoxides with terminal alkynes could be achieved by using a copper catalyst system and chiral anionic tridentate ligands.…”

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confidence: 99%

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Photoinduced Copper-Catalyzed Regio- and Enantioselective Alkynylation of Epoxides

Li,

Cui

et al. 2024

ACS Catal.

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Epoxides are privileged and valuable electrophiles frequently utilized as versatile building blocks in synthetic chemistry to prepare diverse alcohols through ring-opening reactions. However, the catalytic stereoconvergent cross-coupling of racemic epoxides with electro-or nucleophiles has remained a persistent challenge. In this work, we present a mild method to achieve the regio-and enantioselective alkynylation of epoxides with various alkynes, resulting in the synthesis of β-chiral homopropargyl alcohols via a photoinduced copper-based catalytic system. The use of a monofluoro-substituted non-C 2 symmetric bisoxazoline diphenylamine ligand played a pivotal role in the success of this chemistry, with its distinct electronic and steric effects proving crucial in enhancing both reactivity and stereoselectivity. Mechanistic studies supported the idea that the reaction underwent regioselective nucleophilic ring-opening of epoxides with iodides, followed by stereoconvergent radical cross-coupling with alkynes. Notably, the hydroxyl group generated from the ring-opening of epoxide may play an auxiliary role in achieving high enantioselectivity.

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Section: Mechanistic Studiesmentioning

confidence: 54%

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confidence: 99%

Photoinduced Copper-Catalyzed Regio- and Enantioselective Alkynylation of Epoxides

Li,

Cui

et al. 2024

ACS Catal.

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“…Meanwhile, the Liu's group also designed and synthesized a new series of chiral guanidine hybrid ligands, which bear three N‐coordinating subunits (guanidine, amide, and pyridine) (Scheme 19). [ 32 ] The ligands were also successfully applied to Cu(I)‐catalyzed asymmetric Sonogashira C(sp 3 )–C(sp) cross‐coupling between diverse racemic secondary alkyl bromides and terminal alkynes, resulting in good yields and enantioselectivities (up to 96% yield and 91% e.e.). In terms of controlling enantioselectivity, the amino acid backbone, the angle of the bridge, and the substitutions of guanidine and pyridine are important factors that create a chiral environment for the enantioselective construction of the C(sp 3 )–C(sp) bond.…”

Section: Copper Catalyzed Enantioconvergent Substitutions By Carbon N...mentioning

confidence: 99%

Copper Catalyzed Enantioconvergent Nucleophilic Substitutions^†

Huang,

Wan,

Zhu

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryAs a versatile earth‐abundant transition metal, Cu has long been widely applied in the C‐C and C‐X bond forming reactions. As for now, low‐valent Cu(I) is known to reduce the redox active electrophiles via an SET pathway to give the corresponding radical and Cu(II) species. The resulting Cu(II) species can interact with the radical via the out‐sphere pathway, affording the coupling product. Alternatively, Cu(II) can trap the radical through the inner‐sphere process to generate Cu(III) species and then realize challenging bond formations due to the facile reductive elimination of Cu(III) intermediate. Although copper catalysis has been widely applied in arylations of various nucleophiles, copper‐catalyzed enantioconvergent nucleophilic substitutions of racemic alkyl electrophiles have been less explored, likely due to the difficulties in overcoming the reduction potential of alkyl electrophiles, elimination side reactions, and enantiomeric control. In order to overcome the high reduction potential of alkyl electrophiles, the photo‐induced strategy has been developed under mild conditions. An alternative strategy with new anionic tridentate ligands has also been reported in this regard. This review summarizes recent developments in copper‐catalyzed enantioconvergent nucleophilic substitutions of alkyl electrophiles by various nucleophiles to realize C‐N, C‐C, C‐B, C‐P and C‐O bond formations and their brief mechanistic studies.This article is protected by copyright. All rights reserved.

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“…In 2022, Xiaohua Liu and co-workers developed a Cu(I)catalyzed asymmetric Sonogashira C(sp 3 )-C(sp) cross-coupling reaction (Scheme 27). 34 A type of new chiral nitrogen donor hybrid ligand bearing acyclic guanidine, amide, and pyridine subunits was designed. The reaction between diverse racemic secondary alkyl bromides and terminal alkynes proceeded smoothly to afford the coupling products in good efficiency and enantioselectivity.…”

Section: Scheme 25 Carboxamide-directed Stereospecific Couplings Of C...mentioning

confidence: 99%

Recent Advances in Transition-Metal-Catalyzed Sonogashira Cross-Coupling Reactions of Alkyl Electrophiles

Liu,

Zhao

2023

Synthesis

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Catalytic Sonogashira cross-coupling reactions represent an efficient and versatile approach for constructing complex alkynes from readily available starting materials. Despite notable progress in this field, the development of transition-metal-catalyzed Sonogashira cross-coupling reactions of alkyl electrophiles remains limited. This limitation primarily stems from the low reactivity and pronounced propensity of these compounds towards β-H elimination. To overcome these challenges, researchers have investigated the use of palladium, nickel, and copper catalysts for Sonogashira reactions of alkyl electrophiles. Furthermore, significant strides have been made in achieving asymmetric Sonogashira cross-coupling reactions of electrophiles. This short review provides an overview of recent breakthroughs in this area.1 Introduction2 Palladium-Catalyzed Sonogashira Cross-Coupling of Alkyl Halides3 Nickel-Catalyzed Sonogashira Cross-Coupling of Alkyl Halides4 Copper-Catalyzed Sonogashira Cross-Coupling of Alkyl Electrophiles4.1 Copper-Catalyzed Racemic Sonogashira Cross-Coupling of Alkyl Electrophiles4.2 Copper-catalyzed Asymmetric Sonogashira Cross-Coupling of Alkyl Electrophiles5 Conclusions and Perspectives

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Asymmetric Sonogashira C(sp³)–C(sp) bond coupling enabled by a copper(i) complex of a new guanidine-hybrid ligand

Abstract: A type of new chiral nitrogen-donor hybrid ligands bearing acyclic guanidine, amide, and pyridine subunits was rationalized for asymmetric Sonogashira C(sp3)-C(sp) cross-coupling. In connection with CuI, the reaction between diverse...

Cited by 13 publications

References 53 publications

Photoinduced Copper-Catalyzed Regio- and Enantioselective Alkynylation of Epoxides

Photoinduced Copper-Catalyzed Regio- and Enantioselective Alkynylation of Epoxides

Copper Catalyzed Enantioconvergent Nucleophilic Substitutions^†

Recent Advances in Transition-Metal-Catalyzed Sonogashira Cross-Coupling Reactions of Alkyl Electrophiles

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Asymmetric Sonogashira C(sp3)–C(sp) bond coupling enabled by a copper(i) complex of a new guanidine-hybrid ligand

Abstract: A type of new chiral nitrogen-donor hybrid ligands bearing acyclic guanidine, amide, and pyridine subunits was rationalized for asymmetric Sonogashira C(sp3)-C(sp) cross-coupling. In connection with CuI, the reaction between diverse...

Cited by 13 publications

References 53 publications

Photoinduced Copper-Catalyzed Regio- and Enantioselective Alkynylation of Epoxides

Photoinduced Copper-Catalyzed Regio- and Enantioselective Alkynylation of Epoxides

Copper Catalyzed Enantioconvergent Nucleophilic Substitutions†

Recent Advances in Transition-Metal-Catalyzed Sonogashira Cross-Coupling Reactions of Alkyl Electrophiles

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Product

Resources

About

Asymmetric Sonogashira C(sp³)–C(sp) bond coupling enabled by a copper(i) complex of a new guanidine-hybrid ligand

Copper Catalyzed Enantioconvergent Nucleophilic Substitutions^†