Development of Brønsted Base–Photocatalyst Hybrid Systems for Highly Efficient C–C Bond Formation Reactions of Malonates with Styrenes

Baś, Sebastian; Yamashita, Yasuhiro; Kobayashi, Shū

doi:10.1021/acscatal.0c02716

Cited by 33 publications

(17 citation statements)

References 29 publications

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“…In 2020, Yamashita, Kobayashi, and Baś reported a C(sp 3 )–H alkylation reaction between malonate diesters and styrenes via generation and addition of a 1,3-dicarbonyl radical across the alkene acceptor ( Scheme 162 ). 466 Optimal conditions consisted of photocatalyst 4CzIPN , or the related 3DPA2FBN , and KO t -Bu Brønsted base co-catalyst in MeCN solvent under blue-light irradiation. The authors reported 33 examples of this transformation with yields ranging from 17% to 99%.…”

Section: O -Centered Radical Generation From O–h Bonds Through Photochemical and Electrochemical Pcet Processesmentioning

confidence: 99%

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

et al. 2021

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We present here a review of the photochemical and electrochemical applications of multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms in which both an electron and a proton are exchanged together, often in a concerted elementary step. As such, MS-PCET can function as a non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from a wide variety of common organic functional groups. We present an introduction to MS-PCET and a practitioner’s guide to reaction design, with an emphasis on the unique energetic and selectivity features that are characteristic of this reaction class. We then present chapters on oxidative N–H, O–H, S–H, and C–H bond homolysis methods, for the generation of the corresponding neutral radical species. Then, chapters for reductive PCET activations involving carbonyl, imine, other X=Y π-systems, and heteroarenes, where neutral ketyl, α-amino, and heteroarene-derived radicals can be generated. Finally, we present chapters on the applications of MS-PCET in asymmetric catalysis and in materials and device applications. Within each chapter, we subdivide by the functional group undergoing homolysis, and thereafter by the type of transformation being promoted. Methods published prior to the end of December 2020 are presented.

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Section: O -Centered Radical Generation From O–h Bonds Through Photochemical and Electrochemical Pcet Processesmentioning

confidence: 99%

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

et al. 2021

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“…In 2020, they reported a dual catalytic system of Brønsted base and visible light for the reaction of malonate with less electrophilic olefins (Scheme 53). The alkylation reaction is of mild transition metal free condition and high atom economy [201] . First, the photocatalyst was excited by visible light to generate [PC]*, which oxidized the enol form 160 to excited state 161 .…”

Section: Combining Brønsted Base Catalysis With Photoredox Catalysismentioning

confidence: 99%

“…The alkylation reaction is of mild transition metal free condition and high atom economy. [201] First, the photocatalyst was excited by visible light to generate…”

Section: Combining Brønsted Base Catalysis With Photoredox Catalysismentioning

confidence: 99%

Advanced Synthesis Using Photocatalysis Involved Dual Catalytic System

Guo

Wang

et al. 2022

Eur J Org Chem

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Combining visible‐light photoredox catalysis with other kinds of catalysis is a powerful strategy to address the barriers met in reactions driven by single catalyst. Under environmentally benign condition, photoredox catalysis produces radical species via visible light irradiation. These species then work with other catalysts, often resulting in unconventional reactivities, by which the scope of reaction could be expanded. Interest focusing on photocatalysis in the synthetic chemistry community has grown tremendously over the past five years, and one of the most striking emerging features is the development of dual catalytic approaches. This minireview summarizes the progress on this theme, mainly including dual catalytic systems merging photoredox activation with acid/base catalysts.

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“…Very recently, the group of Yamashita and Kobayashi developed a C−C coupling reaction between malonates and styrenes [56] . The reactions were performed at room temperature in MeCN as the solvent under irradiation with blue LEDs (Scheme 42).…”

Section: Cyanoarene‐based Organophotocatalystsmentioning

confidence: 99%

Acridinium Salts and Cyanoarenes as Powerful Photocatalysts: Opportunities in Organic Synthesis

Tlili

Lakhdar

2021

Angewandte Chemie

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The use of organic photocatalysts has revolutionized the field of photoredox catalysis, as it allows access to reactivities that were traditionally restricted to transition‐metal photocatalysts. This Minireview reports recent developments in the use of acridinium ions and cyanoarene derivatives in organic synthesis. The activation of inert chemical bonds as well as the late‐stage functionalization of biorelevant molecules are discussed, with a special focus on their mechanistic aspects.

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Development of Brønsted Base–Photocatalyst Hybrid Systems for Highly Efficient C–C Bond Formation Reactions of Malonates with Styrenes

Cited by 33 publications

References 29 publications

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Advanced Synthesis Using Photocatalysis Involved Dual Catalytic System

Acridinium Salts and Cyanoarenes as Powerful Photocatalysts: Opportunities in Organic Synthesis

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