Photocatalytic, modular difunctionalization of alkenes enabled by ligand-to-metal charge transfer and radical ligand transfer

Chemical Science, Journal Year: 2023, Volume and Issue: 15(1), P. 124 - 133

Published: Nov. 24, 2023

Simple iron salts are able to photocatalyze the diazidation, dichlorination, and fluorochlorination of alkenes via merger ligand-to-metal charge transfer (LMCT) either radical ligand (RLT) or fluorine atom (FAT).

Language: Английский

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Decarboxylative halogenation of aliphatic carboxylic acids catalyzed by iron salts under visible light

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(20), P. 2764 - 2767

Published: Jan. 1, 2024

A general method of visible light-induced decarboxylative halogenation aliphatic carboxylic acids catalyzed by iron is developed.

Language: Английский

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Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

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Mild Amide Synthesis Using Nitrobenzene under Neutral Conditions

Organic Letters, Journal Year: 2022, Volume and Issue: 24(26), P. 4766 - 4771

Published: June 27, 2022

Amide synthesis is one of the most important transformations in organic chemistry due to broad application pharmaceutical drugs and materials. In this report, we describe a mild protocol for amide formation using readily available nitroarenes as nitrogen sources an inexpensive iron complex catalyst. Because use pH-neutral conditions avoidance strong oxidant or reductant, wide range aromatic aliphatic aldehydes well with various functional groups could be tolerated well. A plausible mechanism proposed based on detailed studies, which catalyst initiates radical process solvent plays key role O-atom acceptor.

Language: Английский

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Photoinduced iron-catalyzed C–H alkylation of polyolefins

Chemical Science, Journal Year: 2023, Volume and Issue: 14(35), P. 9374 - 9379

Published: Jan. 1, 2023

Chemically introducing diverse polar groups into polyolefins via carbon-hydrogen bond alkylation with olefins is of substantial value in the synthesis next-generation lightweight thermoplastics, which still underdeveloped. In this work, we report a new approach for efficient commodity using photoinduced iron catalysis. Various could be functionalized broad scope. Polar incorporated single step. The controllable multi-polar functional achieved by designed module-assembled process. Remarkably, even low levels functionalization upcycle polyolefin materials to exhibit unusual physical properties, such as enhancement transparencies, strains, stresses at break materials, and hydrophilicity.

Language: Английский

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Minisci reaction of heteroarenes and unactivated C(sp³)–H alkanes via a photogenerated chlorine radical

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(12), P. 1637 - 1640

Published: Jan. 1, 2023

Minisci reaction of heteroarenes and unactivated C(sp 3 )–H alkanes via a photogenerated chlorine radical from FeCl seawater.

Language: Английский

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Photoinduced Difunctionalization of Diazenes Enabled by N–N Radical Coupling

Organic Letters, Journal Year: 2023, Volume and Issue: 25(36), P. 6671 - 6676

Published: Aug. 29, 2023

In this study, a metal-free difunctionalization strategy for diazenes was developed using range of bifunctionalization reagents. This involves unique N(sp3)–N(sp2) radical coupling between the hydrazine and imine radical. More than 30 triazane core motifs were constructed by installing imines various functional groups, including alkyl, phenyl, cyanoalkyl, sulfonyl on both ends nitrogen–nitrogen bond in an efficient manner.

Language: Английский

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Remote C(sp³)–H heteroarylation of N-fluorocarboxamides with quinoxalin-2(1H)-ones under visible-light-induced photocatalyst-free conditions

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(24), P. 9475 - 9481

Published: Jan. 1, 2022

A photocatalyst-free visible-light-promoted remote C(sp 3 )–H heteroarylation of N -fluoroamides with quinoxalin-2(1 H )-ones was developed. All types δ-C(sp bonds in the could be site-specific activated through 1,5-HAT process.

Language: Английский

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Photoinduced Fe-catalyzed bromination and iodination of unstrained cyclic alcohols

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(14), P. 3692 - 3696

Published: Jan. 1, 2022

A practical protocol for the synthesis of remote bromo- or iodoalkyl ketones via an Fe( iii )-catalysis is reported.

Language: Английский

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Visible-Light-Promoted Fe(III)-Catalyzed N–H Alkylation of Amides and N-Heterocycles

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(15), P. 9797 - 9805

Published: July 20, 2022

The combination of the radical chemistry ligand-to-metal charge transfer with metal catalysis by a single iron salt helps to realize visible-light-promoted N-H alkylation amides and N-heterocycles. A wide variety nitrogen-containing heterocycles were tolerated in our protocol give N-alkylated products. applicability this was further demonstrated late-stage N-H-containing pharmaceuticals. Moreover, N-H-alkylated α-amino tetrahydrofurans could be transformed into versatile ring-opened amino alcohols under reducing conditions. mechanistic study revealed that hydrogen atom tert-butoxyl chlorine responsible for activation C(sp3)-H precursors.

Language: Английский

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