Energy transfer photocatalysis: exciting modes of reactivity

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(3), P. 1068 - 1089

Published: Jan. 1, 2024

Leveraging light energy to expose the ‘dark’ reactive states describes whole essence of triplet–triplet transfer. This offers an impressive opportunity conduct a multitude diverse reactions and access sought-after molecular motifs.

Language: Английский

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Direct electrochemical synthesis of arenesulfonyl fluorides from nitroarenes: a dramatic ionic liquid effect

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(6), P. 3435 - 3440

Published: Jan. 1, 2024

A practical electrosynthesis of aryl sulfonyl fluorides from nitroarenes is described. Cheap N -methylimidazolium p -toluenesulfonate has been found to be an effective additive, promoting the desired fluorosulfonylation under very mild conditions.

Language: Английский

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γ-Amino Alcohols via Energy Transfer Enabled Brook Rearrangement

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10899 - 10907

Published: April 3, 2024

In the long-standing quest to synthesize fundamental building blocks with key functional group motifs, photochemistry in recent past has comprehensively established its attractiveness. Amino alcohols are not only functionally diverse but ubiquitous biologically active realm of compounds. We developed bench-stable bifunctional reagents that could then access sparsely reported γ-amino directly from feedstock alkenes through energy transfer (EnT) photocatalysis. A designed 1,3-linkage across is made possible by intervention a radical Brook rearrangement takes place downstream EnT-mediated homolysis our reagent(s). combination experimental mechanistic investigations and detailed computational studies (DFT) indicates chain propagated reaction pathway.

Language: Английский

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Photosensitized Imino-Thiocyanation of Alkenes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

A metal-free photosensitized 1,2-imino-thiocyanation of olefins has been established by using the easily accessible bifunctional reagent S-cyano-N-(diphenylmethylene) thiohydroxylamine. wide range were successfully transformed into corresponding β-iminothiocyanates in moderate to high yields. This protocol stands out for its nature, broad substrate compatibility, and atom step economy, providing an effective strategy assembling β-amino thiocyanate-containing scaffolds.

Language: Английский

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Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1854 - 1941

Published: Jan. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Language: Английский

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Metal-Free Photoinduced Acylboration of [1.1.1]Propellane via Energy Transfer Catalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9542 - 9549

Published: July 5, 2023

Highly strained 1,3-disubstituted bicyclo[1.1.1]pentanes (BCPs) have been established as bioisosteres of para-disubstituted benzene because they impart valuable pharmacokinetic properties. Herein, we demonstrate an energy transfer-mediated protocol for acylboration [1.1.1]propellanes that allows the direct construction various carbonyl species, such carbamoyl-, carboxyl-, and acyl-, in tandem with synthetically versatile pinacol boronate (Bpin) groups onto BCP substructure under simple reaction conditions. Moreover, drug-like molecules containing boronates are further submitted to late-stage functionalization events. Several important transformations Bpin functional group boronates, including photoinduced cross-coupling reactions BCP-BF3K, derived from BCP-Bpin, were successfully performed showcase synthetic utility. Additionally, diverse elaborate mechanistic investigations provide insights, a plausible mechanism is proposed.

Language: Английский

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Linkage Chemistry of S(VI) Fluorides

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(33)

Published: March 24, 2023

Sulfur(VI)-fluoride exchange linkage as a next generation of click chemistry was introduced by Sharpless and coworkers in 2014. Distinguished from CuAAC, the SuFEx reaction proceeds under metal-free conditions, reactive linkers are variable, enabling access to diverse class compounds. Therein, series emerged has been widely prevalent fields. The SVI -F bond comparison -Cl features excellent stability chemoselectivity. primarily involves formation S-O S-N bonds via commercially available phenols amines, yet less study on C-SuFEx linkage. This review will focus three types for comprising S-O, S-N, S-C bonds, we hope provide practical guidance chemistry.

Language: Английский

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Visible-Light-Mediated Energy Transfer Enables Cyclopropanes Bearing Contiguous All-Carbon Quaternary Centers

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9806 - 9816

Published: July 11, 2023

Cyclopropanes bearing contiguous all-carbon quaternary centers continue to attract attention due their bioactivities. However, methods obtain cyclopropanes with remain largely unexplored the high steric hindrance of these compounds. Herein, we report a visible-light-mediated energy-transfer (EnT) strategy realize in situ donor/donor carbenes from readily available N-tosylhydrazones, facilitating synthesis highly congested EWG-free cyclopropanes. Through this approach, are rapidly installed into complex bioactive molecules, fluorescent and other useful building blocks that challenging synthesize. Detailed mechanistic reactions DFT studies clearly demonstrated role photosensitizer, formation carbenes, necessity light base system.

Language: Английский

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1,2‐Difunctionalization of Acetylene Enabled by Light

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(16)

Published: Feb. 27, 2023

Although the direct conversion of gaseous acetylene into value-added liquid commodity chemicals is becoming increasingly attractive, majority established methodologies are focused on cross-coupling, hydro-functionalization, and polymerization. Herein, we describe a 1,2-difunctionalization method that inserts directly readily available bifunctional reagents. This provides access to diverse C2-linked 1,2-bis-heteroatom products in high regio- stereoselectivity along with opening up previously unexplored synthetic directions. In addition, demonstrate this method's potential by converting obtained functionalized molecules chiral sulfoxide-containing bidentate ligands. Using combination experimental theoretical methods, mechanism for insertion reaction was investigated.

Language: Английский

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Photocatalytic 1,2-Iminosulfonylation and Remote 1,6-Iminosulfonylation of Olefins

Organic Letters, Journal Year: 2023, Volume and Issue: 25(10), P. 1742 - 1747

Published: March 8, 2023

A new class of iminosulfonylation reagents were developed and extensively used in the 1,2-iminosulfonylation various olefins. Olefins containing bioactive molecules, such as indomethacin, gemfibrozil, clofibrate, fenbufen, afforded desired products synthetically useful yields. Furthermore, first remote 1,6-iminosulfonylation alkenes was realized by using oxime ester bifunctionalization reagents. Overall, more than 40 structurally diverse β-imine sulfones obtained moderate to excellent

Language: Английский

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