Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P^V‐Center**

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(35)

Опубликована: Июнь 17, 2022

We present herein the synthesis of a nearly square-pyramidal chlorophosphorane supported by tetradentate bis(amidophenolate) ligand, N,N'-bis(3,5-di-tert-butyl-2-phenoxy)-1,2-phenylenediamide. After chloride abstraction resulting phosphonium cation efficiently promotes disproportionation 1,2-diphenylhydrazine to aniline and azobenzene. Mechanistic studies, spectroscopic analyses theoretical calculations suggest that this unprecedented reactivity mode for P

Язык: Английский

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Organophosphorus-Catalyzed “Dual-Substrate Deoxygenation” Strategy for C–S Bond Formation from Sulfonyl Chlorides and Alcohols/Acids

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(13), С. 8628 - 8635

Опубликована: Июнь 9, 2023

A green method to construct C-S bonds using sulfonyl chlorides and alcohols/acids via a PIII/PV═O catalytic system is reported. The organophosphorus-catalyzed umpolung reaction promotes us propose the "dual-substrate deoxygenation" strategy. Herein, we adopt strategy, which achieves deoxygenation of synthesize thioethers/thioesters driven by redox cycling. represents an operationally simple approach stable phosphine oxide as precatalyst shows broad functional group tolerance. potential application this protocol demonstrated late-stage diversification drug analogues.

Язык: Английский

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Recent Developments and Challenges in the Enzymatic Formation of Nitrogen–Nitrogen Bonds

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 310 - 342

Опубликована: Дек. 17, 2024

The biological formation of nitrogen–nitrogen (N–N) bonds represents intriguing reactions that have attracted much attention in the past decade. This interest has led to an increasing number N–N bond-containing natural products (NPs) and related enzymes catalyze their (referred this review as NNzymes) being elucidated studied greater detail. While more detailed information on biosynthesis NPs, which only become available recent years, provides unprecedented source biosynthetic enzymes, potential for biocatalytic applications been minimally explored. With review, we aim not provide a comprehensive overview both characterized NNzymes hypothetical biocatalysts with putative bond forming activity, but also highlight from perspective. We present compare conventional synthetic approaches linear cyclic hydrazines, hydrazides, diazo- nitroso-groups, triazenes, triazoles allow comparison enzymatic routes via these functional groups. Moreover, pathways well diversity reaction mechanisms are presented according direct groups currently accessible enzymes.

Язык: Английский

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N–N Bond Formation by a Small-Ring Phosphine Catalyst via the P^III/P^V Cycle: Mechanistic Study and Guidelines to Obtain a Good Catalyst

ACS Catalysis, Год журнала: 2023, Номер 13(9), С. 6452 - 6461

Опубликована: Апрель 26, 2023

The mechanism of the N–N cross-coupling nitroarene and aniline catalyzed by 1,2,2,3,4,4-hexamethylphosphetane oxide (1PO) as well prediction a better catalyst was theoretically investigated using DFT DLPNO-CCSD(T) calculations. An active species 1P is generated through deoxygenation 1PO diphenylsilane. Then, extracts one oxygen atom from to produce nitrosoarene. In this step, [3 + 1] cheletropic addition rate-determining step with ΔG0≠ ΔG0 values 28.8 −7.3 kcal/mol, respectively. Next, nitrosoarene exclusively undergoes dehydrative condensation reaction form an azo-cation intermediate, which origin high selectivity in reaction. 2,4,6-trimethylbenzoic acid plays essential role significantly reduce value 41.1 14.8 kcal/mol. Subsequently, reacts azo cation stable hydrazinylphosphonium nucleophilic attack phosphorus cationic nitrogen atom. phosphonium center preferably accepts hydroxyl group water ensure formation hydrazine subsequent step. highest occupied molecular orbital (HOMO) important role. small-ring scaffold raises HOMO energy compared acyclic compounds achieve activity 1P. Substitution dimethylamino for methyl predicted improve further increasing energy.

Язык: Английский

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A Catalytic Method to Activate Nitromethane by the Cooperation of Homo‐ and Heterogeneous Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(7)

Опубликована: Дек. 22, 2023

The achievement of directly activating and utilizing bulk small molecules has remained a longstanding objective in the field chemical synthesis. present work reports catalytic activation method for nitromethane (MeNO

Язык: Английский

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