Photocatalytic Dehydrogenative Cross‐Coupling of Alkenes with Alcohols or Azoles without External Oxidant

Hong, Yi; Niu, Linbin; Song, Chunlan; Li, Yiying; Dou, Bowen; Singh, Atul K.; Lei, Aiwen

doi:10.1002/anie.201609274

Cited by 167 publications

(62 citation statements)

References 66 publications

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“…The resulting radical combines with the halide with concurrent electron transfer back to [eosin Y disodium] + or Co(III), thus, regenerating the catalyst or Co(II). 15 Then, the intermediate 3a is eliminated, giving compound C, which undergoes SET (single electron transfer) reduction to generate the alkyl radical. 16 Oxidation of the alkyl radical by [eosin Y disodium] + generates carbocation E, accompanied by formation of the catalyst.…”

Section: Resultsmentioning

confidence: 99%

Carboxylation of styrenes with CBr₄and DMSO via cooperative photoredox and cobalt catalysis

2017

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Section: Resultsmentioning

confidence: 99%

Carboxylation of styrenes with CBr₄and DMSO via cooperative photoredox and cobalt catalysis

2017

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“…In 2017, Lei reported the first merger of photoredox and cobalt catalysis to achieve alkenylation reactions. They utilized Co(dmgH) 2 ClPy in conjunction with an acridinium‐based photocatalyst (Mes‐Acr‐Me + ) to initiate the cross‐coupling of styrenyl derivatives with various oxygen‐ and nitrogen‐based nucleophiles (Scheme ) …”

Section: Merging Photosensitizers and Cobaloximes In Small‐moleculmentioning

confidence: 99%

Cobaloxime‐Catalyzed Hydrogen Evolution in Photoredox‐Facilitated Small‐Molecule Functionalization

2019

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The development of efficient, mild, economical, and low‐waste processes is a cornerstone of sustainable chemistry. One such synthetic strategy that exemplifies these characteristics is the use of catalytic dehydrogenation in small‐molecule functionalization. This has been achieved in recent history through the use of photoredox catalysis in conjunction with cobaloximes, a class of catalysts that are capable of proton reduction. This has allowed for a variety of bond formations to be achieved with few to no stoichiometric additives while often producing hydrogen gas as the sole stoichiometric by‐product. Herein, select advancements made in this area of sustainable chemistry and catalysis are detailed and the mechanistic insights this body of work has provided thus far are evaluated. As such, this review aims to aid in the further development and study of synthetic strategies involving photoredox‐promoted hydrogen evolution.

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“…若以玻碳电极为阳极及阴极, 2,2′-二氨基联芳烃可由苯胺衍生物经交叉偶联放氢反应高效制备(图 8) [25] . 此外, 徐海超等 [26] 实现了丙二酸酯酰胺的分子图 6 可见光催化交叉偶联放氢反应构筑 C sp2 -C sp2 键 Figure 6 Visible-light-driven CCHE reactions for the construction of C sp2 -C sp2 bonds 图 7 光引发的羧酸脱羧反应 [27] 、醇 [28] 的放氢交叉偶联, 为醛酮及烯醇醚的制备提供了一条廉价、清洁、高效的途径. 由于反应涉及水、醇对烯烃正离子自由基的亲核进攻, C-O 键的生成表现出反马氏的区域选择性.…”

Section: 环境的污染;unclassified

Cross-Coupling Hydrogen Evolution Reactions

Dong¹,

Liu²,

Wu³

2020

Acta Chim. Sinica

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During the past decade, transition metal-catalyzed dehydrogenative cross-couplings have emerged as an attractive strategy in synthetic chemistry due to its high step-and atom-economy as well as the less functionalized coupling partners. However, such reactions have to always use stoichiometric amount of sacrificial oxidants such as peroxides, high-valent metals (Cu salts, Ag salts, etc.), or iodine(III) oxidants, thereby leading to possible generation of toxic wastes and making the process less desirable from a green chemistry perspective. The recently developed photocatalytic CCHE (cross-coupling hydrogen-evolution) reactions are a conceptually new type of reactions enabled by combination of photo-redox catalysis and proton reduction catalysis, wherein the photocatalyst uses light energy as the driving force for the cross-coupling and the hydrogen evolution catalyst may capture electrons and protons from the substrates or reaction intermediates to produce molecular hydrogen (H 2). Thus, without use of any sacrificial oxidant and under mild conditions, the dual catalyst system may afford cross-coupling products with excellent yields and an equivalent amount of H 2 as the sole byproduct. This kind of cross-coupling delivers a greener synthetic strategy and is particularly useful for reactions that involve species sensitive to traditional oxidants. In CCHE reactions, the raw materials are directly converted into products and hydrogen, the reactions are highly atom economy, environmentally friendly, and have attractive potential industrial application prospects. In this review, recent dramatic developments of photocatalytic and electrochemical CCHE reactions are discussed via the most prominent mechanistic pathways, the types of CC bond, C-X (heteroatom) bond, or X-X bond formations and specific reaction classes.

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Photocatalytic Dehydrogenative Cross‐Coupling of Alkenes with Alcohols or Azoles without External Oxidant

Cited by 167 publications

References 66 publications

Carboxylation of styrenes with CBr₄and DMSO via cooperative photoredox and cobalt catalysis

Carboxylation of styrenes with CBr₄and DMSO via cooperative photoredox and cobalt catalysis

Cobaloxime‐Catalyzed Hydrogen Evolution in Photoredox‐Facilitated Small‐Molecule Functionalization

Cross-Coupling Hydrogen Evolution Reactions

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Photocatalytic Dehydrogenative Cross‐Coupling of Alkenes with Alcohols or Azoles without External Oxidant

Cited by 167 publications

References 66 publications

Carboxylation of styrenes with CBr4and DMSO via cooperative photoredox and cobalt catalysis

Carboxylation of styrenes with CBr4and DMSO via cooperative photoredox and cobalt catalysis

Cobaloxime‐Catalyzed Hydrogen Evolution in Photoredox‐Facilitated Small‐Molecule Functionalization

Cross-Coupling Hydrogen Evolution Reactions

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Product

Resources

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Carboxylation of styrenes with CBr₄and DMSO via cooperative photoredox and cobalt catalysis

Carboxylation of styrenes with CBr₄and DMSO via cooperative photoredox and cobalt catalysis