Visible light-promoted reactions with diazo compounds: a mild and practical strategy towards free carbene intermediates

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(19), P. 6833 - 6847

Published: Jan. 1, 2020

Carbenes are important intermediates in organic chemistry and have been widely applied various types of reactions, ranging from cycloaddition reactions sigmatropic rearrangements to C-H functionalizations, thus allowing the rapid construction densely functionalized molecules. Over past decades, remarkable progress has achieved metal-catalyzed carbene transfer reactions. Nevertheless, realizing these transformations under milder and/or greener conditions is still highly desirable. Only recently, visible light-promoted diazo compounds via free emerged as a practical, mild powerful tool. In this tutorial review, we summarize latest advances area, aiming at providing clear overview on reaction design, mechanistic scenarios potential future developments.

Language: Английский

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Lightening Diazo Compounds?

ACS Sustainable Chemistry & Engineering, Journal Year: 2021, Volume and Issue: 9(27), P. 8895 - 8918

Published: June 25, 2021

The development of new sustainable reactions and protocols is essential to fulfill the growing demands every branch organic chemistry for greener synthetic methodologies. In this context, use visible light as only source energy highly appealing. Since diazo compounds are valuable reagents in synthesis, their transformations realized a manner interest. High reactivity easy availability make them suitable solar-driven transformations. Indeed, photochemical have recently proven alternative transition metal catalysis. perspective, we highlight applications these under irradiation, particularly focusing on recent advancements. These include generation carbenes radicals which involve many relevant reactions, [2+1]-cycloadditions, X–H C–H insertions, Wolff rearrangement, more. Mechanistic aspects processes briefly addressed give readers deeper understanding rules underlying photoreactivity compounds. We conclude by emphasizing significant advancements discussing challenges future developments photochemistry reagents.

Language: Английский

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Unlocking novel reaction pathways of diazoalkanes with visible light

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(17), P. 2788 - 2798

Published: Jan. 1, 2022

In this feature article, the photolysis and dye-sensitized reactions of diazoalkanes are discussed applications in organic synthesis presented.

Language: Английский

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Visible Light-Induced Reactions of Diazo Compounds and Their Precursors

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(11), P. 7214 - 7261

Published: May 16, 2024

In recent years, visible light-induced reactions of diazo compounds have attracted increasing attention in organic synthesis, leading to improvement existing reactions, as well the discovery unprecedented transformations. Thus, photochemical or photocatalytic generation both carbenes and radicals provide milder tools toward these key intermediates for many valuable However, vast majority transformations represent new reactivity modes compounds, which are achieved by decomposition photoredox catalysis. particular, use a redox-active photocatalysts opens avenue plethora radical reactions. The application methods led inaccessible classical associated with metal carbenes. most cases, act sources but can also serve acceptors. Importantly, described processes operate under mild, practical conditions. This Review describes this subfield compound chemistry, particularly focusing on advancements.

Language: Английский

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Visible light-mediated photolysis of organic molecules: the case study of diazo compounds

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(48), P. 7346 - 7360

Published: Jan. 1, 2023

This article discusses the photochemistry of several diazo compounds undergoing visible light-mediated photolysis to generate free carbenes (or other highly reactive intermediates), which can be sequentially trapped by different reacting partners.

Language: Английский

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C–H Functionalization Reactions of Unprotected N-Heterocycles by Gold-Catalyzed Carbene Transfer

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(17), P. 9925 - 9931

Published: Aug. 7, 2020

The C–H functionalization reaction of N-heterocycles with an unprotected N–H group is one the most step-economic strategies to introduce functional groups without need for installation and removal protecting groups. Despite recent significant advances in chemistry, this strategy remains unsatisfactorily developed. In report, we disclose a simple straightforward protocol allow selective double-benzannellated via gold-catalyzed carbene-transfer reactions (29 examples, up 86% yield). scope can also be expanded corresponding protected heterocycles (37 98% yield), further demonstrating generality method. Mechanistic studies by density theory (DFT) calculations underpin importance gold catalyst reveal that selectivity driven trace amounts water present mixture.

Language: Английский

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Visible Light-Promoted Transformation of Diazo Compounds via the Formation of Free Carbene as Key Intermediate

Chinese Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 41(12), P. 4565 - 4565

Published: Jan. 1, 2021

Carbene is one of the most important synthetic intermediates in organic synthesis.In past few decades, transition-metal catalyzed carbene transfer reactions have made remarkable development.Recently, visible light-promoted transformation diazo compounds through formation free as key intermediate begun to rise.The reaction only need light sole energy source which meets concept green chemistry.Since pioneering works developed by groups Diaves and Zhou, photo-promoted has attracted more attentions.On basis previous work, latest progress this field further improved, mainly focuses on recent new under irradiation contributions reported from Chinese research group.The future development direction, well challenges prospected.

Language: Английский

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Late-stage azolation of benzylic C‒H bonds enabled by electrooxidation

Science China Chemistry, Journal Year: 2021, Volume and Issue: 64(5), P. 800 - 807

Published: March 19, 2021

Language: Английский

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Visible-Light-Mediated Formal Carbene Insertion Reaction: Enantioselective Synthesis of 1,4-Dicarbonyl Compounds Containing All-Carbon Quaternary Stereocenter

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(9), P. 5510 - 5516

Published: April 25, 2022

We developed an efficient visible-light-mediated formal carbene insertion reaction of 1,3-diketones with diazoesters for the construction enantioenriched 1,4-dicarbonyl compounds a quaternary carbon center. Combining visible light and Brønsted acid catalyst, chiral were achieved in good yields high enantioselectivities by photochemical transfer protocol.

Language: Английский

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Visible-light-induced organocatalytic enantioselective N–H insertion of α-diazoesters enabled by indirect free carbene capture

Chemical Science, Journal Year: 2022, Volume and Issue: 14(4), P. 843 - 848

Published: Nov. 29, 2022

While asymmetric insertion of metal carbenes into H-X (X = C, N, O, etc.) bonds has been well-established, control over free is challenging due to the presence strong background reactions and lack any anchor for a catalyst interaction. Here we have achieved first photo-induced metal-free bond this type. With visible light used as promoter chiral phosphoric acid catalyst, α-diazoesters aryl amines underwent smooth N-H form enantioenriched α-aminoesters with high efficiency good enantioselectivity under mild conditions. Key success was use DMSO an additive, which served rapidly capture highly reactive carbene intermediate domesticated sulfoxonium ylide.

Language: Английский

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