Visible Light-Induced Transition Metal Catalysis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1543 - 1625

Published: Oct. 8, 2021

In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which led to the discovery of unprecedented transformations well improvement known reactions. this subfield complex serves double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via single catalytic cycle, thus contrasting established dual photocatalysis an exogenous photosensitizer is employed. addition, approach often synergistically combines catalyst–substrate interaction with photoinduced process, feature that uncommon conventional photoredox chemistry. This Review describes early development advances emerging field.

Language: Английский

---

Visible light-driven organic photochemical synthesis in China

Science China Chemistry, Journal Year: 2018, Volume and Issue: 62(1), P. 24 - 57

Published: Dec. 21, 2018

Language: Английский

---

Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(17), P. 9790 - 9833

Published: Aug. 6, 2020

Alkyl radicals are key intermediates in organic synthesis. Their classic generation from alkyl halides has a severe drawback due to the employment of toxic tin hydrides point that "flight tyranny tin" radical processes was considered for long time an unavoidable issue. This review summarizes main alternative approaches unstabilized radicals, using photons as traceless promoters. The recent development photochemical and photocatalyzed enabled discovery plethora new precursors, opening world chemistry broader community, thus allowing era photon democracy.

Language: Английский

---

Recent advances in nucleophile-triggered CO₂-incorporated cyclization leading to heterocycles

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 48(1), P. 382 - 404

Published: Nov. 27, 2018

CO₂, as a sustainable, feasible, abundant one-carbon synthon, has been utilized in carboxylative cyclization, carbonylative and reductive cyclization.

Language: Английский

---

Transition Metal-Catalyzed Organic Reactions under Visible Light: Recent Developments and Future Perspectives

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(16), P. 9170 - 9196

Published: July 20, 2020

The development of transition metal (TM) catalysis for organic synthesis under visible light without recourse to typical photoredox catalysts has become a rapidly growing area research and been actively explored in the past several years. Distinct from extensively developed catalysis, which photocatalyst generally does not directly participate bond-forming process, photocatalyst/TM synergistic absorbs photon energy transfers TM catalyst through redox or transfer this Review focuses on summarizing recent developments photocatalytic reactions that use complexes both absorb catalytic bond formation involving covalently bonded intermediate. contents are categorized by used (Pd, Cu, Co, Ni, Mn, Au, Rh, Fe, Ru), with descending sequence according number examples reported each metal, provide an overview April 2020. Future perspectives personal opinions regarding expanding field also discussed.

Language: Английский

---

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(10), P. 2518 - 2531

Published: May 6, 2021

ConspectusCarbon dioxide (CO2) is not only a greenhouse gas and common waste product but also an inexpensive, readily available, renewable carbon resource. It important one-carbon (C1) building block in organic synthesis for the construction of valuable compounds. However, its utilization challenging owing to thermodynamic stability kinetic inertness. Although significant progress has been achieved, many limitations remain this field with regard substrate scope, reaction system, activation strategies.Since 2015, our group focused on CO2 synthesis. We are interested vast possibilities radical chemistry, although high reactivity radicals presents challenges controlling selectivity. hope develop highly useful transformations involving by achieving balance selectivity under mild conditions. Over past 6 years, we along other experts have disclosed radical-type carboxylative cyclizations carboxylations using CO2.We initiated research realizing Cu-catalyzed oxytrifluoromethylation allylamines heteroaryl methylamines generate 2-oxazolidones various precursors. Apart from Cu catalysis, visible-light photoredox catalysis powerful method achieve efficient cyclization. In these cases, single-electron-oxidation-promoted C–O bond formation between benzylic carbamates key step.Since carboxylic acids exist widely natural products bioactive drugs serve as bulk chemicals industry, realized further visible-light-promoted construct such chemicals. achieved selective umpolung imines, enamides, tetraalkylammonium salts, oxime esters successive single-electron-transfer (SSET) reduction. Using strategy, dearomative arylcarboxylation indoles CO2. addition incorporation 1 equiv per substrate, recently developed photoredox-catalyzed dicarboxylation alkenes, allenes, (hetero)arenes via SSET reduction, which allows two molecules into compounds diacids polymer precursors.In two-electron CO2, sought new strategies realize single-electron Inspired hypothetical electron-transfer mechanism iron–sulfur proteins, visible-light-driven thiocarboxylation alkenes catalytic iron salts promoters. The in-situ-generated Fe/S complexes likely able reduce anion, could react give stabilized radical. Moreover, charge-transfer complex (CTC) thiolate acrylate/styrene hydrocarboxylation generation or alkene anion. On basis novel CTC, organocatalytic Hantzsch ester effective reductant.

Language: Английский

---

Catalysis with Palladium Complexes Photoexcited by Visible Light

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(34), P. 11586 - 11598

Published: Jan. 2, 2019

Abstract Palladium catalysis induced by visible light is an emerging field of catalysis. In contrast to classical reactions catalyzed Pd complexes in the ground state, which mostly proceed through two‐electron redox processes, mechanisms these new methods based on photoexcited usually operate transfer a single electron. Such processes lead putative hybrid Pd/radical species, exhibit both radical and Pd‐type reactivity. This Minireview highlights recent progress this rapidly growing area.

Language: Английский

---

Visible-Light-Driven Reductive Carboarylation of Styrenes with CO₂ and Aryl Halides

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(18), P. 8122 - 8129

Published: April 20, 2020

The first example of visible-light-driven reductive carboarylation styrenes with CO2 and aryl halides in a regioselective manner has been achieved. A broad range iodides bromides were compatible this reaction. Moreover, pyridyl halides, alkyl even chlorides also viable method. These findings may stimulate the exploration novel Meerwein arylation-addition reactions user-friendly as radical sources photocatalytic utilization CO2.

Language: Английский

---

Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(49), P. 20661 - 20670

Published: Nov. 24, 2020

Electrochemistry grants direct access to reactive intermediates (radicals and ions) in a controlled fashion toward selective organic transformations. This feature has been demonstrated variety of alkene functionalization reactions, most which proceed via an anodic oxidation pathway. In this report, we further expand the scope electrochemistry reductive alkenes. particular, strategic choice reagents reaction conditions enabled radical-polar crossover pathway wherein two distinct electrophiles can be added across highly chemo- regioselective fashion. Specifically, used strategy intermolecular carboformylation, anti-Markovnikov hydroalkylation, carbocarboxylation alkenes—reactions with rare precedents literature—by means electroreductive generation alkyl radical carbanion intermediates. These reactions employ readily available starting materials (alkyl halides, alkenes, etc.) simple, transition-metal-free display broad substrate good tolerance functional groups. A uniform protocol achieve all three transformations by simply altering medium. development provides new avenue for constructing Csp3–Csp3 bonds.

Language: Английский

---

Photoredox Catalysis as a Strategy for CO₂ Incorporation: Direct Access to Carboxylic Acids from a Renewable Feedstock

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(17), P. 5492 - 5502

Published: July 23, 2018

Carbon dioxide is an attractive reagent for organic synthesis from the standpoint of global sustainability. Its widespread use, however, hampered by fact that it poorly reactive. New catalysts and technologies enable C-C bond constructions are thus high intrinsic value. This Minireview describes recent advances in area photoredox catalysis as enabling strategy promoting carboxylations.

Language: Английский

---