Cu-Catalyzed Enantioselective Alkylarylation of Vinylarenes Enabled by Chiral Binaphthyl–BOX Hybrid Ligands DOI
Shunya Sakurai, Akira Matsumoto, Taichi Kano

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(45), P. 19017 - 19022

Published: Oct. 5, 2020

Transition-metal-catalyzed radical relay coupling reactions have recently emerged as one of the most powerful methods to achieve difunctionalization olefins. However, there has been limited success in applying this method asymmetric catalysis using an effective chiral ligand. Herein we report Cu-catalyzed enantioselective alkylarylation vinylarenes alkylsilyl peroxides alkyl sources. This reaction proceeds under practical conditions and affords 1,1-diarylalkane structures that are found a variety bioactive molecules. Notably, highly was accomplished by combining bis(oxazoline) ligands with binaphthyl scaffolds.

Language: Английский

The Persistent Radical Effect in Organic Synthesis DOI
Dirk Leifert, Armido Studer

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

Citations

652

Toolbox for Distal C–H Bond Functionalizations in Organic Molecules DOI

Soumya Kumar Sinha,

Srimanta Guin,

Sudip Maiti

et al.

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

Citations

389

Enantioselective Radical Reactions Using Chiral Catalysts DOI
Shovan Mondal, Frédéric Dumur, Didier Gigmès

et al.

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

Citations

266

Catalytic cascade reactions by radical relay DOI
Huan‐Ming Huang, Monserrat H. Garduño‐Castro,

Charlotte Morrill

et al.

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

Citations

245

Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes DOI
Song Lu, Niankai Fu, Brian G. Ernst

et al.

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

Published: June 29, 2020

Language: Английский

Citations

245

Copper-catalyzed radical relay in C(sp3)–H functionalization DOI
Zuxiao Zhang, Pinhong Chen, Guosheng Liu

et al.

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

Citations

236

Enantioselective C H Bond Functionalizations by 3d Transition-Metal Catalysts DOI
Łukasz Woźniak, Nicolai Cramer

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

Published: April 20, 2019

Language: Английский

Citations

216

Metallaphotoredox catalysis for sp3C–H functionalizations through hydrogen atom transfer (HAT) DOI
Jingchang Zhang, Magnus Rueping

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

Citations

98

Enantioselective Construction of Quaternary All-Carbon Centers via Copper-Catalyzed Arylation of Tertiary Carbon-Centered Radicals DOI
Lianqian Wu, Fei Wang, Pinhong Chen

et al.

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

Citations

122

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

Emily N. Pinter,

Silas P. Cook

et al.

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

Citations

120