Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics DOI
Heng Song, Shen Yang,

Hu Zhou

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(8), P. 5303 - 5314

Published: April 1, 2022

Triggering C-N bond formation with nitroaromatics and boronic acids at mild conditions is highly desirable, since most prior works were carried out under harsh sometimes suffered from poor chemo- or regioselectivity. Herein, a low-valent-tungsten-catalyzed reaction that enables the ambient temperature amination of disclosed. With readily available W(CO)6 as precatalyst external-photosensitizer-free conditions, smoothly undergo coupling reactions their acid partners, delivering structurally diverse secondary amines in good yields (>50 examples, up to 96%). This methodology both scalable chemoselective engages aliphatic aromatic partners. The catalysis initiated by deoxygenation trans-[W(CO)4(PPh3)2] (trans-W, PPh3 = triphenylphosphine) complex, which forms situ via ligand replacement.

Language: Английский

Native Amides as Enabling Vehicles for Forging sp3–sp3 Architectures via Interrupted Deaminative Ni-Catalyzed Chain-Walking DOI Creative Commons
Jesus Rodrigalvarez, Hao Wang, Rubén Martı́n

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 3869 - 3874

Published: Feb. 8, 2023

Herein, we disclose an interrupted deaminative Ni-catalyzed chain-walking strategy that forges sp3-sp3 architectures at remote, yet previously unfunctionalized, methylene sp3 C-H sites enabled by the presence of native amides. This protocol is characterized its mild conditions and wide scope, including challenging substrate combinations. Site-selectivity can be dictated a judicious choice ligand, thus offering opportunity to enable bond formations are otherwise inaccessible in conventional events.

Language: Английский

Citations

57
Nickel‐Catalyzed Switchable Site‐Selective Alkene Hydroalkylation by Temperature Regulation** DOI
Jia‐Wang Wang, Deguang Liu, Zhe Chang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 25, 2022

Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickel-catalyzed switchable site-selective hydroalkylation. The selection of reaction temperatures leads to protocols provide regiodivergent hydroalkylated products single substrate. This protocol allows convenient synthesis α- and β-branched protected amines, both which are important fields pharmaceutical chemistry biochemistry. In addition, enantioenriched alkylamines can be accessed in catalytic asymmetric variant. Preliminary mechanistic studies indicate formation more stable nickelacycle provides driving force migration. thermodynamic kinetic properties different reduction elimination intermediates responsible for site-selectivity.

Language: Английский

Citations

66
Ligand‐Controlled NiH‐Catalyzed Regiodivergent Chain‐Walking Hydroalkylation of Alkenes DOI
Lei Zhao,

Yuqin Zhu,

Mengyuan Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(30)

Published: May 24, 2022

Abstract A NiH‐catalyzed migratory hydroalkylation of alkenyl amines with predictable and switchable regioselectivity is reported. By utilizing a ligand‐controlled, directing group‐assisted strategy, various alkyl units are site‐selectively installed at inert sp 3 C−H sites far away from the original C=C bonds. range structurally diverse α‐ β‐branched protected conveniently synthesized via stabilization 5‐ 6‐membered nickelacycles respectively. This method exhibits broad scope high functional group tolerance, can be applied to late‐stage modification medicinally relevant molecules.

Language: Английский

Citations

53
Orthogonal Access to α‐/β‐Branched/Linear Aliphatic Amines by Catalyst‐Tuned Regiodivergent Hydroalkylations DOI
Pengfei Yang, Wei Shu

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(34)

Published: June 21, 2022

Abstract Linear, α‐branched, and β‐branched aliphatic amines are widespread in pharmaceuticals, agrochemicals, fine chemicals. Thus, the development of direct efficient methods to these structures a tunable manner is highly desirable yet challenging. Herein, catalyst‐controlled synthesis linear from Ni/Co‐catalyzed regio‐ site‐selective hydroalkylations alkenyl with alkyl halides developed. This catalytic protocol features reliable prediction control coupling position alkylation provide orthogonal access identical starting materials. platform unlocks reactivity selectivity nickel hydride cobalt chemistry catalytically repurpose three types under mild conditions.

Language: Английский

Citations

50
Low-valent tungsten redox catalysis enables controlled isomerization and carbonylative functionalization of alkenes DOI
Tanner C. Jankins,

William C. Bell,

Yu Zhang

et al.

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(6), P. 632 - 639

Published: June 1, 2022

Language: Английский

Citations

40
Synergistic Hydrocobaltation and Borylcobaltation Enable Regioselective Migratory Triborylation of Unactivated Alkenes DOI
Yinsong Zhao, Shaozhong Ge

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(14)

Published: Jan. 28, 2022

The structural diversity of sp3 -triorganometallic reagents enhances their potentiality in the modular construction molecular complexity chemical synthesis. Despite significant achievements on preparation 1,1,1- and 1,1,2-triorganometallic B,B,B-reagents, catalytic approaches that enable installation multiple boryl groups at skipped carbons unactivated alkenes still remain elusive. Herein, we report a cobalt-catalyzed selective triborylation reaction to access synthetically versatile 1,1,3-triborylalkanes. This protocol provides general platform for regioselective trifunctionalization alkenes, its utility is highlighted by synthesis various value-added chemicals from readily accessible alkenes. Mechanistic studies, including deuterium-labelling experiments evaluation potential reactive intermediates, provide insight into experimentally observed chemo- regioselectivity.

Language: Английский

Citations

39
Unleashing the potentiality of metals: synergistic catalysis with light and electricity DOI
Zhengjia Shen, Jia‐Lin Tu, Binbin Huang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 4024 - 4040

Published: Jan. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

Language: Английский

Citations

13
Stereodivergent, Kinetically Controlled Isomerization of Terminal Alkenes via Nickel Catalysis DOI Creative Commons
Camille Rubel, Anne K. Ravn, Hang Chi Ho

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 18, 2024

Abstract Because internal alkenes are more challenging synthetic targets than terminal alkenes, metal‐catalyzed olefin mono‐transposition (i.e., positional isomerization) approaches have emerged to afford valuable E ‐ or Z‐ from their complementary alkene feedstocks. However, the applicability of these methods has been hampered by lack generality, commercial availability precatalysts, and scalability. Here, we report a nickel‐catalyzed platform for stereodivergent / Z ‐selective synthesis at room temperature. Commercial reagents enable this one‐carbon transposition ‐internal via Ni−H‐mediated insertion/elimination mechanism. Though mechanistic regime is same in both systems, underlying pathways that lead each active catalysts distinct, with catalyst forming comproportionation an oxidative addition complex followed substrate protonation metal trialkylphosphonium salt additive. In case, ligand sterics denticity control stereochemistry prevent over‐isomerization.

Language: Английский

Citations

12
Palladium‐Catalyzed Inward Isomerization Hydroaminocarbonylation of Alkenes DOI

Xian‐Jin Zou,

Zhao‐Xing Jin,

Huiyi Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)

Published: April 15, 2024

In contrast to the kinetically favored outward isomerization-hydrocarbonylation of alkenes, disfavored inward alkenes remains an important challenge. Herein, we have developed a novel and effective palladium-catalyzed isomerization-hydroaminocarbonylation unactivated aniline hydrochlorides for formation synthetically valuable α-aryl carboxylic amides in high yields site-selectivities. The efficiency reaction is attributed relay catalysis strategy, which Markovnikov-favored [PdH]-P

Language: Английский

Citations

11
Remote Site‐Selective Asymmetric Protoboration of Unactivated Alkenes Enabled by Bimetallic Relay Catalysis DOI
Qiao Zhang, Simin Wang, Jianjun Yin

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(23)

Published: March 17, 2022

Abstract A remote C(sp 3 )−H bond asymmetric borylation of unactivated alkenes was achieved by bimetallic relay catalysis. The reaction proceeded through reversible and consecutive β‐H elimination/olefin insertion promoted CoH species generated in situ, followed copper‐catalyzed protoboration. use this synergistic Co/Cu catalysis protocol allowed the enantioselective protoboration various terminal internal alkenes, as well an unrefined mixture olefin isomers, at distal less‐reactive β‐position to a functional group, leading chiral organoboronates.

Language: Английский

Citations

35