Ni(I)–X Complexes Bearing a Bulky α-Diimine Ligand: Synthesis, Structure, and Superior Catalytic Performance in the Hydrogen Isotope Exchange in Pharmaceuticals DOI
Cayetana Zárate, Haifeng Yang, Máté J. Bezdek

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(12), P. 5034 - 5044

Published: March 2, 2019

The synthesis and spectroscopic characterization of a family Ni–X (X = Cl, Br, I, H) complexes supported by the bulky α-diimine chelate N,N′-bis(1R,2R,3R,5S)-(−)-isopinocampheyl-2,3-butanediimine (ipcADI) are described. Diimine-supported, three-coordinate nickel(I)–X have been proposed as key intermediates in host catalytic transformations such C–C C–heteroatom cross-coupling C–H functionalization but until now remained synthetically elusive. A combination structural, spectroscopic, electrochemical, computational studies were used to establish electronic structure each monomeric [(ipcADI)NiX] I) complex nickel(I) derivative redox-neutral chelate. dimeric nickel hydride, [(ipcADI)Ni(μ2-H)]2, was prepared characterized X-ray diffraction; however, magnetic measurements 1H NMR spectroscopy support monomer formation at ambient temperature THF solution. This hydride precatalyst for hydrogen isotope exchange (HIE) bonds arenes pharmaceuticals. By virtue multisite reactivity high efficiency, new provided unprecedented specific activities (50–99 Ci/mmol) radiolabeling, meeting threshold required radioligand binding assays. Use air-stable readily synthesized precursor, [(ipcADI)NiBr2], broad functional group tolerance, compatibility with polar protic solvents additional assets nickel-catalyzed HIE method.

Language: Английский

Electrochemically driven cross-electrophile coupling of alkyl halides DOI
Wen Zhang, Lingxiang Lu,

Wendy Zhang

et al.

Nature, Journal Year: 2022, Volume and Issue: 604(7905), P. 292 - 297

Published: Feb. 21, 2022

Language: Английский

Citations

237
Mechanism of Ni-Catalyzed Reductive 1,2-Dicarbofunctionalization of Alkenes DOI
Qiao Lin, Tianning Diao

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(44), P. 17937 - 17948

Published: Oct. 7, 2019

Ni-catalyzed cross-electrophile coupling reactions have emerged as appealing methods to construct organic molecules without the use of stoichiometric organometallic reagents. The mechanisms are complex: plausible pathways, such "radical chain" and "sequential reduction" mechanisms, dependent on sequence activation electrophiles. A combination kinetic, spectroscopic, studies reveals that a Ni-catalyzed, reductive 1,2-dicarbofunctionalization alkenes proceeds through pathway. reduction Ni by Zn is turnover-limiting step, consistent with Ni(II) intermediates catalyst resting-state. only sufficient reduce (phen)Ni(II) Ni(I) species. As result, commonly proposed Ni(0) absent under these conditions. (Phen)Ni(I)–Br selectively activates aryl bromides via two-electron oxidation addition, whereas alkyl activated (phen)Ni(I)–Ar single-electron afford radicals. These findings could provide insight into achieving selectivity between different

Language: Английский

Citations

232
Site-Selective Catalytic Deaminative Alkylation of Unactivated Olefins DOI
Shang‐Zheng Sun, Ciro Romano, Rubén Martı́n

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(41), P. 16197 - 16201

Published: Sept. 29, 2019

A catalytic deaminative alkylation of unactivated olefins is described. The protocol characterized by its mild conditions, wide scope, including the use ethylene as substrate, and exquisite site-selectivity pattern for both α-olefins internal olefins, thus unlocking a new platform to forge sp3-sp3 linkages, even in context late-stage functionalization.

Language: Английский

Citations

221
NiH‐Catalyzed Remote Asymmetric Hydroalkylation of Alkenes with Racemic α‐Bromo Amides DOI

Fang Zhou,

Yao Zhang,

Xianfeng Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(6), P. 1754 - 1758

Published: Dec. 12, 2018

Reported here is a terminal-selective, remote asymmetric hydroalkylation of olefins with racemic α-bromo amides. The reaction proceeds by NiH-catalyzed alkene isomerization and subsequent alkylation reaction, can enantioconvergently introduce an unsymmetrical secondary alkyl group from amide onto terminal C(sp3 )-H position along the hydrocarbon chain alkene. This mild process affords range structurally diverse chiral α-alkylalkanoic amides in excellent yields, high regio- enantioselectivities. In addition, synthetic utility this protocol further highlighted regioconvergent conversion industrial raw materials isomeric olefin mixtures into enantioriched on large scale.

Language: Английский

Citations

187
Nickel‐Catalyzed Electrochemical Reductive Relay Cross‐Coupling of Alkyl Halides to Aryl Halides DOI

Ke‐Jin Jiao,

Dong Liu,

Hong‐Xing Ma

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(16), P. 6520 - 6524

Published: Dec. 3, 2019

A highly regioselective Ni-catalyzed electrochemical reductive relay cross-coupling between an aryl halide and alkyl has been developed in undivided cell. Various functional groups are tolerated under these mild reaction conditions, which provides alternative approach for the synthesis of 1,1-diarylalkanes.

Language: Английский

Citations

186
Tackling Remote sp3 C−H Functionalization via Ni‐Catalyzed “chain‐walking” Reactions DOI
Daniel Janßen-Müller, Basudev Sahoo, Shang‐Zheng Sun

et al.

Israel Journal of Chemistry, Journal Year: 2019, Volume and Issue: 60(3-4), P. 195 - 206

Published: Aug. 21, 2019

Abstract Nickel catalysts have recently played an important role for rapidly and reliably converting feedstock chemicals into valuable compounds of interest both pharmaceutical academic laboratories. Herein, we summarize the recent advances on ability nickel to trigger olefin isomerization via “chain‐walking”, causing a displacement catalyst throughout alkyl chain while opening up new grounds forging C−C C‐heteroatom linkages at remote, yet unfunctionalized, sp 3 C−H bonds.

Language: Английский

Citations

184
Nickel-catalyzed formation of quaternary carbon centers using tertiary alkyl electrophiles DOI
Weichao Xue, Xiao Jia, Xuan Wang

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(6), P. 4162 - 4184

Published: Jan. 1, 2021

This review provides a comprehensive summary of recent advances in nickel-catalyzed reactions employing tertiary alkyl electrophiles for the construction quaternary carbon centers.

Language: Английский

Citations

176
Nickel-Catalyzed Enantioconvergent Reductive Hydroalkylation of Olefins with α-Heteroatom Phosphorus or Sulfur Alkyl Electrophiles DOI

Shi-Jiang He,

Jia‐Wang Wang, Yan Li

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 142(1), P. 214 - 221

Published: Dec. 15, 2019

Substantial advances in enantioconvergent C(sp3)–C(sp3) bond formation reactions have been made recent years through the use of transition-metal-catalyzed cross-coupling racemic secondary alkyl electrophiles with organometallic reagents. Herein, we report a general process for asymmetric construction alkyl–alkyl bonds adjacent to heteroatoms, namely, nickel-catalyzed reductive hydroalkylation olefins α-heteroatom phosphorus or sulfur electrophiles. Including readily available olefins, this reaction has considerable advantages, such as mild conditions, broad substrate scope, and good functional group compatibility, making it desirable alternative traditional electrophile–nucleophile reactions.

Language: Английский

Citations

169
Enantioselective C(sp3)–C(sp3) cross-coupling of non-activated alkyl electrophiles via nickel hydride catalysis DOI
Srikrishna Bera, Runze Mao, Xile Hu

et al.

Nature Chemistry, Journal Year: 2020, Volume and Issue: 13(3), P. 270 - 277

Published: Dec. 30, 2020

Language: Английский

Citations

168
Hydroalkylation of Olefins To Form Quaternary Carbons DOI

Samantha A. Green,

Tucker R. Huffman, Ruairí O. McCourt

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(19), P. 7709 - 7714

Published: April 29, 2019

Metal-hydride hydrogen atom transfer (MHAT) functionalizes alkenes with predictable branched (Markovnikov) selectivity. The breadth of these transformations has been confined to π-radical traps; no sp3 electrophiles have reported. Here we describe a Mn/Ni dual catalytic system that hydroalkylates unactivated olefins alkyl halides, yielding aliphatic quaternary carbons.

Language: Английский

Citations

165