Pincer‐Type Ligand‐Assisted Catalysis and Small‐Molecule Activation by non‐VSEPR Main‐Group Compounds DOI
Subrata Kundu

Chemistry - An Asian Journal, Journal Year: 2020, Volume and Issue: 15(20), P. 3209 - 3224

Published: Aug. 14, 2020

In 2005, a facile dihydrogen activation was reported by the Power group using an alkyne analog of germanium [ArGe≡GeAr; Ar=2,6-Trip2 -C6 H3 (Trip=2,4,6-i Pr3 H2 )]. After that, significant progress has been made in various small molecules main-group compounds, and variety stoichiometric catalytic processes have formulated p-block elements. this regard, compounds containing low-valent elements with frontier orbitals relatively energy gaps or forming frustrated Lewis pair (FLP) became quite successful. spite these promising transformations, redox-cycling catalysts based on remain extremely rare. Recently, it observed that pincer type ligands supported geometry constrained are capable acting as redox similar to those transition metals. review, we focus synthesis structural aspects ligands. Emphasis placed their applications activity activation.

Language: Английский

Dual role of nitroarenes as electrophiles and arylamine surrogates in Buchwald–Hartwig-type coupling for C–N bond construction DOI Creative Commons

Zhiguo Lei,

Jiaxin Yao, Yuxuan Xiao

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(10), P. 3552 - 3561

Published: Jan. 1, 2024

A reductive and denitrative amination of nitroarenes has been developed, allowing the highly selective synthesis various di- triarylamines. The protocol employed synthetically upstream as both electrophiles amine sources.

Language: Английский

Citations

13
Transition-metal-, oxidant- and additive-free multi-component synthesis of alkyl heteroaryl BCPs enabled by visible-light-induced phosphine-catalyzed halogen-atom transfer DOI
Jun Xu,

Yu Hong,

Ruiyuan Xu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

This study describes a pioneering visible-light-induced phosphine-catalyzed halogen-atom transfer (XAT) strategy that heralds new era in the difunctionalization of [1.1.1]propellane.

Language: Английский

Citations

12
Recent progress in the synthesis of N-substituted arylamines by reductive cross-coupling of nitroarenes DOI

Jing‐Hao Qin,

Wang Yao,

Jun-Yao Ouyang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(9), P. 2638 - 2664

Published: Jan. 1, 2024

This review describes the recent advances in different reaction types and catalytic systems for construction of C–NAr S–NAr bonds by nitroaromatic reductive cross-coupling.

Language: Английский

Citations

11
PIII/PV=O Catalyzed Cascade Synthesis of N‐Functionalized Azaheterocycles DOI
Trevor V. Nykaza, Gen Li, Junyu Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(11), P. 4505 - 4510

Published: Dec. 23, 2019

Abstract An organocatalytic method for the modular synthesis of diverse N‐aryl and N‐alkyl azaheterocycles (indoles, oxindoles, benzimidazoles, quinoxalinediones) is reported. The employs a small‐ring organophosphorus‐based catalyst (1,2,2,3,4,4‐hexamethylphosphetane P ‐oxide) hydrosilane reductant to drive conversion ortho ‐functionalized nitroarenes into through sequential intermolecular reductive C−N cross coupling with boronic acids, followed by intramolecular cyclization. This enables rapid construction from readily available building blocks, including regiospecific approach N‐substituted benzimidazoles quinoxalinediones.

Language: Английский

Citations

55
P(III)/P(V)-Catalyzed Methylamination of Arylboronic Acids and Esters: Reductive C–N Coupling with Nitromethane as a Methylamine Surrogate DOI
Gen Li,

Ziyang Qin,

Alexander T. Radosevich

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(38), P. 16205 - 16210

Published: Sept. 4, 2020

The direct reductive N-arylation of nitromethane by organophosphorus-catalyzed C–N coupling with arylboronic acid derivatives is reported. This method operates the action a small ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane P-oxide) together mild terminal reductant hydrosilane to drive selective installation methylamino group (hetero)aromatic boronic acids and esters. also provides for unified synthetic approach isotopically labeled N-methylanilines from various stable isotopologues (i.e., CD3NO2, CH315NO2, 13CH3NO2), revealing this easy-to-handle compound as versatile precursor group.

Language: Английский

Citations

53
Recent Progress on Reductive Coupling of Nitroarenes by Using Organosilanes as Convenient Reductants DOI
Yang Gao, Simin Yang, Yanping Huo

et al.

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(19), P. 3971 - 3986

Published: May 18, 2020

Abstract Nitroarenes are stable, low‐cost, and readily available starting materials. The directly utilize nitroarenes in synthetically valuable C−N bond formation is of great significance, because the pre‐reduction step to corresponding amines can be avoided. Previously, phosphines carbon monoxide (CO) most widely used reductants reductive cyclization or/and carbonylation nitroarenes. Currently, much attention has been attracted organosilanes as new potential reducing agents, not only they inexpensive, easy‐to‐handle, mild reagents, but also various novel reaction models have explored. In this review, we mainly summarize recent progress on coupling by using end reductants. We hope that a deep understanding model underlying working mechanism provide timely guideline for researchers who interested fantastic area, leading further exploration practical efficient N‐heterocycle synthesis. magnified image

Language: Английский

Citations

51
Visible-light-driven Cadogan reaction DOI
Zhonghua Qu, Pu Wang, Xing Chen

et al.

Chinese Chemical Letters, Journal Year: 2021, Volume and Issue: 32(8), P. 2582 - 2586

Published: Feb. 26, 2021

Language: Английский

Citations

45
Cu-Catalyzed Cross-Coupling of Nitroarenes with Aryl Boronic Acids to Construct Diarylamines DOI
Xinyu Guan,

Haoran Zhu,

Tom G. Driver

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(20), P. 12417 - 12422

Published: Sept. 23, 2021

The development and study of a simple copper-catalyzed reaction nitroarenes with aryl boronic acids to form diarylamines that uses phenyl silane as the stoichiometric terminal reductant is described. This cross-coupling requires little 2 mol % CuX 4 mol% diphosphine for success tolerates broad range functional groups on either nitroarene or acid afford amine in good yield. Mechanistic investigations established proceeds via nitrosoarene intermediate copper required catalyze both deoxygenation C-NAr bond formation acid.

Language: Английский

Citations

44
PIII/PV═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines DOI
Gen Li, Steven P. Miller, Alexander T. Radosevich

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(36), P. 14464 - 14469

Published: Sept. 2, 2021

An organophosphorus-catalyzed method for the synthesis of unsymmetrical hydrazines by cross-selective intermolecular N-N reductive coupling is reported. This employs a small ring phosphacycle (phosphetane) catalyst together with hydrosilane as terminal reductant to drive nitroarenes and anilines good chemoselectivity functional group tolerance. Mechanistic investigations support an autotandem catalytic reaction cascade in which organophosphorus drives two sequential mechanistically distinct reduction events via PIII/PV═O cycling order furnish target bond.

Language: Английский

Citations

43
Umpolung strategies for the functionalization of peptides and proteins DOI Creative Commons
Andrew M. White, Isabella R. Palombi, Lara R. Malins

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(10), P. 2809 - 2823

Published: Jan. 1, 2022

This perspective highlights the growing body of literature that leverages polarity reversal (umpolung reactivity) for selective modification proteinogenic functionalities and identifies opportunities further innovation.

Language: Английский

Citations

35