Visible-light-induced iron-catalyzed reduction of nitroarenes to anilines DOI
Shilei Yang, Min He, Yi Wang

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(95), P. 14177 - 14180

Published: Jan. 1, 2023

An efficient visible-light-induced iron-catalyzed reduction of nitroarenes to anilines by using N-ethylmorpholine (NEM) as a reductant under mild conditions has been developed. The reaction proceeds with photosensitizer-free and features good excellent yields broad functional group tolerance. Preliminary mechanistic investigations showed that this was conducted via ligand-to-metal (NEM Fe3+) charge transfer nitro triplet biradical-induced hydrogen atom processes.

Language: Английский

The transition metal-catalysed hydroboration reaction DOI Creative Commons
Stephen J. Geier, Christopher M. Vogels, Jennifer A. Melanson

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(21), P. 8877 - 8922

Published: Jan. 1, 2022

This review covers the development of transition metal-catalysed hydroboration reaction, from its beginnings in 1980s to more recent developments including earth-abundant catalysts and an ever-expanding array substrates.

Language: Английский

Citations

144
Halogen-atom and group transfer reactivity enabled by hydrogen tunneling DOI
Timothée Constantin, Bartosz Górski, Michael J. Tilby

et al.

Science, Journal Year: 2022, Volume and Issue: 377(6612), P. 1323 - 1328

Published: Sept. 15, 2022

The generation of carbon radicals by halogen-atom and group transfer reactions is generally achieved using tin silicon reagents that maximize the interplay enthalpic (thermodynamic) polar (kinetic) effects. In this work, we demonstrate a distinct reactivity mode enabled quantum mechanical tunneling uses cyclohexadiene derivative γ-terpinene as abstractor under mild photochemical conditions. This protocol activates alkyl aryl halides well several alcohol thiol derivatives. Experimental computational studies unveiled noncanonical pathway whereby cyclohexadienyl radical undergoes concerted aromatization or abstraction through an effective H atom. activation mechanism seemingly thermodynamically kinetically unfavorable but rendered feasible tunneling.

Language: Английский

Citations

89
Engineering organic polymers as emerging sustainable materials for powerful electrocatalysts DOI
Xun Cui, Mingjie Wu,

Xueqin Liu

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(3), P. 1447 - 1494

Published: Jan. 1, 2024

A comprehensive overview on organic polymers as electrocatalysts is summarized. By presenting the engineering strategies, insightful understandings, challenges, and perspectives, we hope this review can provide valuable references for readers.

Language: Английский

Citations

41
Beyond 2,5-furandicarboxylic acid: status quo, environmental assessment, and blind spots of furanic monomers for bio-based polymers DOI Creative Commons
Mattia Annatelli, Julián E. Sánchez-Velandia, Giovanna Mazzi

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(16), P. 8894 - 8941

Published: Jan. 1, 2024

This review represents an overview of the status quo furan-based monomers and related bio-based polymers, highlighting key challenges for scaling from lab to pre-industrial levels.

Language: Английский

Citations

17
Recent Advances in the Domain of Cyclic (Alkyl)(Amino) Carbenes DOI Creative Commons
Saroj Kumar Kushvaha, Ankush Mishra, Herbert W. Roesky

et al.

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 17(7)

Published: Jan. 6, 2022

Isolation of cyclic (alkyl) amino carbenes (cAACs) in 2005 has been a major achievement the field stable due to their better electronic properties. cAACs and bicyclic(alkyl)(amino)carbene (BicAAC) essence are most electrophilic as well nucleophilic known till date. Due excellent properties terms character, have utilized different areas chemistry, including stabilization low valent main group transition metal species, activation small molecules, catalysis. The applications catalysis opened up new avenues research cAAC chemistry. This review summarizes results chemistry published until August 2021.

Language: Английский

Citations

66
Chemoselective hydroborative reduction of nitro motifs using a transition-metal-free catalyst DOI

Wubing Yao,

Jiali Wang,

Yinpeng Lou

et al.

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(16), P. 4554 - 4559

Published: Jan. 1, 2021

The first transition-metal-free catalysts for deoxygenative reduction of nitroarenes, nitro heteroarenes and even notoriously challenging nitroalkanes using pinacolborane have been reported.

Language: Английский

Citations

62
Mechanistic Diversity of Low-Valent Chromium Catalysis: Cross-Coupling and Hydrofunctionalization DOI
Xuefeng Cong, Xiaoming Zeng

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(8), P. 2014 - 2026

Published: April 8, 2021

ConspectusTransition-metal catalysis has traditionally been dominated by precious metals because of their high reactivity toward chemical transformations. As a cost-effective alternative, earth-abundant group 6 metal chromium is underdeveloped, and its remains largely unexplored, although the industrially important Phillips catalyst, which composed Cr as active metal, currently used to supply almost 40% total world demand for high-density polyethylene. served in organoreagents with high-valent states (≥2+), are typified reactions involving Nozaki–Hiyama–Kishi (NHK) Takai–Utimoto one-electron transfer processes. Given that low-valent usually facilitate process oxidative addition (OA), studying state provides opportunity develop new However, probably low stability reactive or lack catalytic activity structurally stable complexes, there limited success respect developing promoted Cr. In recent years, our probed adopting strategy forming situ. this Account, we detail efforts study behavior mechanism challenging transformations, such cleavage chemically inert bonds cross-coupling hydrofunctionalization arenes nitro motifs, strategies address prominent selectivity issues. We highlight finding Cr, being formed situ, possesses intriguing ability promote unactivated C–O, C–N, C–H achieve Kumada couplings even enable between two C(aryl)–O/C(aryl)–N bonds. During these processes, adopts high-spin interact chemicals, allowing insertion into σ-bonds. The OA model two-electron rarely considered allows breakage one cycle. This most transition suitable only bond catalysis. Mechanisms unusual, processes more often proposed, exemplified NHK reactions. These provide efficient functionalized benzaldehydes, amides, anilines, amines, levels selectivity. hope account will extend scope cognition

Language: Английский

Citations

60
Methanol as a Potential Hydrogen Source for Reduction Reactions Enabled by a Commercial Pt/C Catalyst DOI
Vishakha Goyal, Tarun Kumar Bhatt,

Chitrarekha Dewangan

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(4), P. 2245 - 2259

Published: Feb. 8, 2023

Catalytic reduction reactions using methanol as a transfer hydrogenating agent is gaining significant attention because this simple alcohol inexpensive and produced on bulk scale. Herein, we report the catalytic utilization of hydrogen source for different functional organic compounds such nitroarenes, olefins, carbonyl compounds. The key to success transformation use commercially available Pt/C catalyst, which enabled hydrogenation series functionalized nitroarenes-to-anilines, alkenes-to-alkanes, aldehydes-to-alcohols both solvent donor. practicability Pt-based protocol showcased by demonstrating catalyst recycling reusability well reaction upscaling. In addition, system was also adaptable N-methylation N-alkylation anilines via borrowing process. This work provides flexible approach prepare variety value-added products from readily methanol, Pt/C, other starting materials.

Language: Английский

Citations

28
Chromium-catalyzed stereodivergent E- and Z-selective alkyne hydrogenation controlled by cyclic (alkyl)(amino)carbene ligands DOI Creative Commons
Liang Ling, Chenyang Hu, Linhong Long

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Feb. 22, 2023

Abstract The hydrogenation of alkynes allows the synthesis olefins, which are important feedstock for materials, pharmaceutical, and petrochemical industry. Thus, methods that enable this transformation via low-cost metal catalysis desirable. However, achieving stereochemical control in reaction is a long-standing challenge. Here, we report on chromium-catalyzed E - Z -selective olefin alkynes, controlled by two carbene ligands. A cyclic (alkyl)(amino)carbene ligand contains phosphino anchor enables trans -addition manner, selectively forming -olefins. With an imino anchor-incorporated ligand, stereoselectivity can be switched, giving mainly -isomers. This ligand-enabled geometrical stereoinversion strategy one overrides common -selectivity with different catalysis, allowing highly efficient on-demand access to both -olefins stereo-complementary fashion. Mechanistic studies indicate steric effect between these ligands may dominate selective or stereochemistry.

Language: Английский

Citations

28
Deoxygenation of Nitrous Oxide and Nitro Compounds Using Bis(N‐Heterocyclic Silylene)Amido Iron Complexes as Catalysts DOI
Xi Chen, Hao Wang,

Shaozhi Du

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(7)

Published: Nov. 12, 2021

Herein, we report the efficient degradation of N2 O with a well-defined bis(silylene)amido iron complex as catalyst. The deoxygenation using silanone 4 catalyst and pinacolborane (HBpin) sacrificial reagent proceeds smoothly at 50 °C to form , H2 (pinB)2 O. Mechanistic studies suggest that iron-silicon cooperativity is key this catalytic transformation, which involves activation, H atom transfer, release oxygenation boron sites. This approach has been further developed enable reductions nitro compounds, producing amino-boranes good functional-group tolerance excellent chemoselectivity.

Language: Английский

Citations

39