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

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

---

Recent Progress on Reductive Coupling of Nitroarenes by Using Organosilanes as Convenient Reductants

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

---

P^III/P^V═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines

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

---

Chemoselective Primary Amination of Aryl Boronic Acids by P^III/P^V═O-Catalysis: Synthetic Capture of the Transient Nef Intermediate HNO

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(20), P. 8902 - 8907

Published: May 12, 2022

A catalytic approach to intercept the transient HNO for a chemoselective primary amination of arylboronic acids is reported. phosphetane-based catalyst operating within PIII/PV═O redox cycling shown capture HNO, generated in situ by Nef decomposition 2-nitropropane, selectively install amino group at aryl Csp2 centers. The method furnishes versatile arylamines from acid substrates with preservation otherwise reactive functional groups.

Language: Английский

---

Enabling Reductive C–N Cross-Coupling of Nitroalkanes and Boronic Acids by Steric Design of P(III)/P(V)═O Catalysts

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(18), P. 8242 - 8248

Published: May 2, 2022

An organophosphorus-catalyzed C–N bond-forming reductive coupling of nitroalkanes with arylboronic acids and esters is reported. The method shows excellent chemoselectivity for the nitro/boronic acid substrate pair, allowing synthesis N-(hetero)arylamines rich in functionalization. identification a sterically reduced phosphetane catalyst capable productive P(III)/P(V)═O redox manifold key enabling development. Combined experimental kinetics computational mechanistic studies show that affects post-rate-limiting steps to enable event preference deleterious side-paths.

Language: Английский

---

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

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

---

Uniting Amide Synthesis and Activation by P^III/P^V–Catalyzed Serial Condensation: Three-Component Assembly of 2-Amidopyridines

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(36), P. 14487 - 14494

Published: Sept. 3, 2021

An organophosphorus (PIII/PV redox) catalyzed method for the three-component condensation of amines, carboxylic acids, and pyridine N-oxides to generate 2-amidopyridines via serial dehydration is reported. Whereas amide synthesis functionalization usually occur under divergent reaction conditions, here a phosphetane catalyst (together with mild bromenium oxidant terminal hydrosilane reductant) shown drive both steps chemoselectively in an auto-tandem catalytic cascade. The ability prepare functionalize amides action single organocatalytic reactive intermediate enables new possibilities efficient modular preparation medicinal targets.

Language: Английский

---

A switchable redox annulation of 2-nitroarylethanols affording N-heterocycles: photoexcited nitro as a multifunctional handle

Chemical Science, Journal Year: 2022, Volume and Issue: 13(37), P. 11074 - 11082

Published: Jan. 1, 2022

A cyclization strategy of 2-nitroarylethanols under blue-light irradiation was developed, which is triggered by a photoexcited nitro-induced double hydrogen atom abstraction ( d -HAA) process, delivering indoles, N –OH oxindoles and –H oxindoles.

Language: Английский

---

Merging excited-state copper catalysis and triplet nitro(hetero)arenes for direct synthesis of 2-aminophenol derivatives

Chem, Journal Year: 2023, Volume and Issue: 10(2), P. 686 - 697

Published: Dec. 11, 2023

Language: Английский

---

Nickel-Catalyzed Reductive Cross-Coupling of N-Acyl and N-Sulfonyl Benzotriazoles with Diverse Nitro Compounds: Rapid Access to Amides and Sulfonamides

Organic Letters, Journal Year: 2021, Volume and Issue: 24(1), P. 58 - 63

Published: Dec. 14, 2021

Herein we report a Ni-catalyzed reductive transamidation of conveniently available N-acyl benzotriazoles with alkyl, alkenyl, and aryl nitro compounds, which afforded various amides good yields broad substrate scope. The same catalytic reaction conditions were also applicable for N-sulfonyl benzotriazoles, could undergo smooth coupling nitroarenes nitroalkanes to afford the corresponding sulfonamides.

Language: Английский

---