Nickel-Catalyzed Multicomponent Coupling: Synthesis of α-Chiral Ketones by Reductive Hydrocarbonylation of Alkenes DOI
Jian Chen, Shaolin Zhu

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(35), P. 14089 - 14096

Published: Aug. 26, 2021

A nickel-catalyzed, multicomponent regio- and enantioselective coupling via sequential hydroformylation carbonylation from readily available starting materials has been developed. This modular hydrofunctionalization strategy enables the straightforward reductive hydrocarbonylation of a broad range unactivated alkenes to produce wide variety unsymmetrical dialkyl ketones bearing functionalized α-stereocenter, including enantioenriched chiral α-aryl α-amino ketones. It uses bisoxazoline as ligand, silane reductant, chloroformate safe CO source, racemic secondary benzyl chloride or an N-hydroxyphthalimide (NHP) ester protected acid alkylation reagent. The benign nature this process renders method suitable for late-stage functionalization complex molecules.

Language: Английский

Electrocatalysis as an enabling technology for organic synthesis DOI
Luiz F. T. Novaes, Jinjian Liu, Yifan Shen

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(14), P. 7941 - 8002

Published: Jan. 1, 2021

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and ion intermediates in controlled fashion under mild conditions inspired development number new electrochemical methodologies preparation valuable chemical motifs. Particularly, recent developments electrosynthesis have featured an use redox-active electrocatalysts further enhance control over selective formation downstream reactivity these intermediates. Furthermore, electrocatalytic mediators enable proceed manner that is mechanistically distinct from purely methods, allowing subversion kinetic thermodynamic obstacles encountered conventional synthesis. This review highlights key innovations within past decade area electrocatalysis, with emphasis on mechanisms catalyst design principles underpinning advancements. A host oxidative reductive are discussed grouped according classification transformation nature electrocatalyst.

Language: Английский

Citations

872
Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts DOI
Cong Ma, Ping Fang,

Zhao‐Ran Liu

et al.

Science Bulletin, Journal Year: 2021, Volume and Issue: 66(23), P. 2412 - 2429

Published: July 13, 2021

Language: Английский

Citations

293
Electrochemically Enabled, Nickel-Catalyzed Dehydroxylative Cross-Coupling of Alcohols with Aryl Halides DOI
Zijian Li, Wenxuan Sun,

Xianxu Wang

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(9), P. 3536 - 3543

Published: Feb. 23, 2021

As alcohols are ubiquitous throughout chemical science, this functional group represents a highly attractive starting material for forging new C–C bonds. Here, we demonstrate that the combination of anodic preparation alkoxy triphenylphosphonium ion and nickel-catalyzed cathodic reductive cross-coupling provides an efficient method to construct C(sp2)–C(sp3) bonds, in which free aryl bromides—both readily available chemicals—can be directly used as coupling partners. This paired electrolysis reaction features broad substrate scope bearing wide gamut functionalities, was illustrated by late-stage arylation several structurally complex natural products pharmaceuticals.

Language: Английский

Citations

202
Recent advances in nickel-catalyzed reductive hydroalkylation and hydroarylation of electronically unbiased alkenes DOI
Xiaoxu Wang, Xi Lu, Yan Li

et al.

Science China Chemistry, Journal Year: 2020, Volume and Issue: 63(11), P. 1586 - 1600

Published: Sept. 28, 2020

Language: Английский

Citations

152
Nickel-catalyzed electrochemical carboxylation of unactivated aryl and alkyl halides with CO2 DOI Creative Commons

Guo‐Quan Sun,

Wei Zhang, Li‐Li Liao

et al.

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

Published: Dec. 6, 2021

Electrochemical catalytic reductive cross couplings are powerful and sustainable methods to construct C-C bonds by using electron as the clean reductant. However, activated substrates used in most cases. Herein, we report a general practical electro-reductive Ni-catalytic system, realizing electrocatalytic carboxylation of unactivated aryl chlorides alkyl bromides with CO2. A variety bromides, iodides sulfonates can also undergo such reaction smoothly. Notably, realize electrochemical (pseudo)halides CO2 avoiding use sacrificial electrodes. Moreover, this economic strategy reductant features mild conditions, inexpensive catalyst, safe cheap electrodes, good functional group tolerance broad substrate scope. Mechanistic investigations indicate that might proceed via oxidative addition halides Ni(0) complex, reduction aryl-Ni(II) adduct Ni(I) species following

Language: Английский

Citations

120
Site-Selective C–H alkylation of Complex Arenes by a Two-Step Aryl Thianthrenation-Reductive Alkylation Sequence DOI Creative Commons

Beatrice Lansbergen,

Paola Granatino,

Tobias Ritter

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(21), P. 7909 - 7914

Published: May 24, 2021

Herein, we present an undirected para-selective two-step C–H alkylation of complex arenes useful for late-stage functionalization. The combination a site-selective thianthrenation with palladium-catalyzed reductive electrophile cross-coupling grants access to diverse range synthetically alkylated which cannot be accessed otherwise comparable selectivity, diversity, and practicality. robustness this transformation is further demonstrated by thianthrenium-based coupling two fragments.

Language: Английский

Citations

116
NiH-catalyzed asymmetric hydroarylation of N-acyl enamines to chiral benzylamines DOI Creative Commons
Yuli He,

Huayue Song,

Jian Chen

et al.

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

Published: Jan. 27, 2021

Enantiomerically pure chiral amines and related amide derivatives are privilege motifs in many pharmacologically active molecules. In comparison to the well-established hydroamination, transition metal-catalysed asymmetric hydrofunctionalization of enamines provides a complementary approach for their construction. Here we report NiH-catalysed enantio- regioselective reductive hydroarylation N-acyl enamines, allowing practical access broad range structurally diverse, enantioenriched benzylamines under mild, operationally simple reaction conditions.

Language: Английский

Citations

113
Facile and general electrochemical deuteration of unactivated alkyl halides DOI Creative Commons
Pengfei Li,

Chengcheng Guo,

Siyi Wang

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: June 30, 2022

Abstract Herein, a facile and general electroreductive deuteration of unactivated alkyl halides (X = Cl, Br, I) or pseudo-halides OMs) using D 2 O as the economical deuterium source was reported. In addition to primary secondary halides, sterically hindered tertiary chlorides also work very well, affording target deuterodehalogenated products with excellent efficiency incorporation. More than 60 examples are provided, including late-stage dehalogenative natural products, pharmaceuticals, their derivatives, all incorporation (up 99% D), demonstrating potential utility developed method in organic synthesis. Furthermore, does not require external catalysts tolerates high current, showing possible use industrial applications.

Language: Английский

Citations

106
Nickel-Catalyzed Enantioselective Electrochemical Reductive Cross-Coupling of Aryl Aziridines with Alkenyl Bromides DOI Creative Commons

Hu Xia,

Iván Cheng‐Sánchez, Sergio Cuesta‐Galisteo

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6270 - 6279

Published: March 7, 2023

An electrochemically driven nickel-catalyzed enantioselective reductive cross-coupling of aryl aziridines with alkenyl bromides has been developed, affording enantioenriched β-aryl homoallylic amines excellent E-selectivity. This electroreductive strategy proceeds in the absence heterogeneous metal reductants and sacrificial anodes by employing constant current electrolysis an undivided cell triethylamine as a terminal reductant. The reaction features mild conditions, remarkable stereocontrol, broad substrate scope, functional group compatibility, which was illustrated late-stage functionalization bioactive molecules. Mechanistic studies indicate that this transformation conforms stereoconvergent mechanism aziridine is activated through nucleophilic halide ring-opening process.

Language: Английский

Citations

89
Electroreductive Cross‐Electrophile Coupling (eXEC) Reactions DOI
Yaowen Liu, Pengfei Li, Yanwei Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: June 16, 2023

Abstract Electrochemistry utilizes electrons as a potent, controllable, and traceless alternative to chemical oxidants or reductants, typically offers more sustainable option for achieving selective organic synthesis. Recently, the merger of electrochemistry with readily available electrophiles has been recognized viable increasingly popular methodology efficiently constructing challenging C−C C‐heteroatom bonds in manner complex molecules. In this mini‐review, we have systematically summarized most recent advances electroreductive cross‐electrophile coupling (eXEC) reactions during last decade. Our focus on electrophiles, including aryl alkyl (pseudo)halides, well small molecules such CO 2 , SO D O.

Language: Английский

Citations

86