The Persistent Radical Effect in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(1), P. 74 - 108

Published: May 22, 2019

Abstract Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if have lifetimes they generated at equal rates, will become dominant process. This high cross‐selectivity based on kinetic phenomenon called persistent radical effect (PRE). In this Review, an explanation PRE supported by simulations simple model systems provided. Radical stabilities discussed within context their lifetimes, various examples PRE‐mediated radical–radical in synthesis summarized. It shown that restricted to coupling with transient radical. If one partner longer‐lived than other radical, operates achieved. important point expands scope chemistry. The Review divided into parts, namely 1) or organic 2) “radical–metal crossover reactions”; here, metal‐centered species more generally transition‐metal complexes able react discussed—a field has flourished recently.

Language: Английский

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Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Language: Английский

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Enantioselective Radical Reactions Using Chiral Catalysts

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 5842 - 5976

Published: Jan. 24, 2022

Benefiting from the impressive increase in fundamental knowledge, last 20 years have shown a continuous burst of new ideas and consequently plethora catalytic methods for enantioselective radical reactions. This review aims to provide complete survey progress achieved over this latter period. The first part focuses on use chiral organocatalysts, these include catalysts covalently linked substrate those that interact with by weaker interactions like hydrogen bonds. second is devoted transition-metal redox catalysis which organized according increasing atomic number first-row transition metals (Ti, Cr, Fe, Mn, Co, Ni, Cu). Bioinspired manganese- iron-mediated hydroxylations oxidations are also discussed. A specific section dedicated reactivity Ru, Rh, Ir complexes as Lewis acids special focus at metal. Absorption photons result different events such energy transfer, single-electron hydrogen-atom transfer facilitating formation radicals. Organocatalysis has been successfully combined photocatalysts, opened pathways enlarging precursors available. merger photocatalysis organo- or metalla-photocatalysis brought novelty allowed discovery large original transformations. enzyme-catalyzed reactions involving intermediates largely benefit visible-light irradiation included review. provides comprehensive inventory goal detailing reaction mechanisms involved transformations any nonspecialist could find their own creativity invent yet unknown applications.

Language: Английский

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Catalytic cascade reactions by radical relay

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 48(17), P. 4626 - 4638

Published: Jan. 1, 2019

Radical cascade reactions are an attractive tool for the rapid construction of complex molecular architectures. Although a large number powerful radical cascades have been developed, stoichiometric amounts reagents and/or additives often required to mediate these processes. relay strategies, in which character is recycled, require only catalytic amount reagent and particularly as they promise that high atom economy. This tutorial review highlights recent advances this rapidly developing area by setting out dissecting reaction designs underpinning state-of-the-art processes involving relays. Advances field will open door more efficient synthesis with far-reaching benefits makers end-users molecules.

Language: Английский

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Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes

Nature Chemistry, Journal Year: 2020, Volume and Issue: 12(8), P. 747 - 754

Published: June 29, 2020

Language: Английский

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Copper-catalyzed radical relay in C(sp³)–H functionalization

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(5), P. 1640 - 1658

Published: Jan. 1, 2022

Radical-involved transition metal (TM) catalysis has greatly enabled new reactivities in recent decades. Copper-catalyzed radical relay offers enormous potential C(sp3)-H functionalization which combines the unique regioselectivity of hydrogen atom transfer (HAT) and versatility copper-catalyzed cross-coupling. More importantly, significant progress been achieved asymmetric C-H through judicious ligand design. This tutorial review will highlight advances this rapidly growing area, we hope survey inspire future strategic developments for selective functionalization.

Language: Английский

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Enantioselective C H Bond Functionalizations by 3d Transition-Metal Catalysts

Trends in Chemistry, Journal Year: 2019, Volume and Issue: 1(5), P. 471 - 484

Published: April 20, 2019

Language: Английский

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Metallaphotoredox catalysis for sp³C–H functionalizations through hydrogen atom transfer (HAT)

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(12), P. 4099 - 4120

Published: Jan. 1, 2023

sp 3 C–H functionalizations under the combination of photocatalytic HAT and transition metal catalysis.

Language: Английский

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Enantioselective Construction of Quaternary All-Carbon Centers via Copper-Catalyzed Arylation of Tertiary Carbon-Centered Radicals

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(5), P. 1887 - 1892

Published: Jan. 22, 2019

An enantioselective copper-catalyzed arylation of tertiary carbon-centered radicals, leading to quaternary all-carbon stereocenters, has been developed herein. The including both benzylic and nonbenzylic were produced by the addition trifluoromethyl radical α-substituted acrylamides, subsequently captured chiral aryl copper(II) species give C–Ar bonds with excellent enantioselectivity. Importantly, an acylamidyl (CONHAr) group adjacent carbon is essential for asymmetric coupling. reaction itself features broad substrate scope, functional compatibility mild conditions.

Language: Английский

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Copper-Catalyzed, N-Directed Csp³–H Trifluoromethylthiolation (−SCF₃) and Trifluoromethylselenation (−SeCF₃)

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(46), P. 18405 - 18410

Published: Nov. 7, 2019

A direct and versatile copper-catalyzed trifluoromethylthiolation trifluoromethylselenation of primary, secondary, tertiary aliphatic C-H bonds was developed. The reaction provides access to molecules containing these emerging moieties in the presence a wide range common functional groups complex molecular environments.

Language: Английский

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