C–H activation

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: June 17, 2021

Language: Английский

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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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Catalytic alkylation of unactivated C(sp³)–H bonds for C(sp³)–C(sp³) bond formation

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 48(18), P. 4921 - 4942

Published: Jan. 1, 2019

This review summarizes recent advancements in catalytic direct transformation of unactivated C(sp³)–H bonds into C(sp³)–C(sp³) bonds.

Language: Английский

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Navigating the Unnatural Reaction Space: Directed Evolution of Heme Proteins for Selective Carbene and Nitrene Transfer

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(5), P. 1209 - 1225

Published: Jan. 25, 2021

ConspectusDespite the astonishing diversity of naturally occurring biocatalytic processes, enzymes do not catalyze many transformations favored by synthetic chemists. Either nature does care about specific products, or if she does, has adopted a different strategy. In cases, appropriate reagents used chemists are readily accessible to biological systems. Here, we discuss our efforts expand catalytic repertoire encompass powerful reactions previously known only in small-molecule catalysis: formation and transfer reactive carbene nitrene intermediates leading broad range including products with bonds biology. light structural similarity iron (Fe═C(R1)(R2)) (Fe═NR) oxo (Fe═O) intermediate involved cytochrome P450-catalyzed oxidation, have precursors that systems encountered repurposed P450s natural world. The resulting protein catalysts fully genetically encoded function intact microbial cells cell-free lysates, where their performance can be improved optimized directed evolution. By leveraging promiscuity P450 enzymes, evolved transferases exhibiting excellent activity toward these new-to-nature reactions. Since initial report 2012, number other heme proteins myoglobins, protoglobins, cytochromes c also been found engineered promote unnatural transfer. Due altered active-site environments, often displayed complementary activities selectivities P450s.Using wild-type proteins, others described selective reactions, cyclopropanation, cyclopropenation, Si–H insertion, B–H C–H insertion. Similarly, variety asymmetric processes aziridination, sulfide imidation, amidation, and, most recently, amination demonstrated. scopes state-of-the-art based on transition-metal catalysts, making biocatalysts valuable addition chemist's toolbox. Moreover, enabled exquisite regio- stereocontrol imposed enzyme catalyst, this platform provides an exciting opportunity address challenging problems modern chemistry catalysis, ones eluded for decades.

Language: Английский

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Recent advances in transition-metal-catalyzed carbene insertion to C–H bonds

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(7), P. 2759 - 2852

Published: Jan. 1, 2022

C-H functionalization has been emerging as a powerful method to establish carbon-carbon and carbon-heteroatom bonds. Many efforts have devoted transition-metal-catalyzed direct transformations of Metal carbenes generated in situ from transition-metal compounds diazo or its equivalents are usually applied the transient reactive intermediates furnish catalytic cycle for new C-C C-X bond formation. Using this strategy unactivated simple alkanes complex molecules can be further functionalized transformed multi-functionalized compounds. In area, carbene insertion bonds paid continuous attention. Diverse catalyst design strategies, synthetic methods, potential applications developed. This critical review will summarize advance dated up July 2021, by categories aliphatic C(sp3)-H, aryl (aromatic) C(sp2)-H, heteroaryl (heteroaromatic) C(sp2)-H bonds, alkenyl alkynyl C(sp)-H, well asymmetric more coverage given recent work. Due rapid development future directions topic also discussed. give authors an overview chemistry with focus on systems

Language: Английский

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3d metallaelectrocatalysis for resource economical syntheses

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(13), P. 4254 - 4272

Published: Jan. 1, 2020

This review summarizes key developments in 3d metallaelectrocatalysis the context of resource economy molecular syntheses.

Language: Английский

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Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(18), P. 10672 - 10714

Published: Aug. 14, 2020

Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development processes that enable efficient synthesis enantiopure compounds unquestionable importance to chemists working within many diverse fields central science. Traditional approaches solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order raise energy one diastereomeric states over other. By contrast, Review examines alternative tactic which a set attractive noncovalent operating are used control enantioselectivity. Examples where creative approach has been successfully applied render fundamental enantioselective presented discussed. In cases examined, ligand scaffold carefully designed accommodate these interactions, while others, critical was only elucidated subsequent computational mechanistic studies. Through exploration discussion recent reports encompassing wide range reaction classes, we hope inspire continue develop asymmetric transformations based powerful concept.

Language: Английский

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Photocatalytic three-component asymmetric sulfonylation via direct C(sp3)-H functionalization

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: April 22, 2021

Language: Английский

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Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

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Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Jan. 20, 2021

Abstract Recently, with the boosted development of radical chemistry, enantioselective functionalization C( sp 3 )–H bonds via a pathway has witnessed renaissance. In principle, two distinct catalytic modes, distinguished by steps in which stereochemistry is determined (the formation step or step), can be devised. This Perspective discusses state-of-the-art area involving intermediates as well future challenges and opportunities.

Language: Английский

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