Phosphorus-Based Catalysis

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(4), P. 536 - 558

Published: March 16, 2021

Phosphorus-based organocatalysis encompasses several subfields that have undergone rapid growth in recent years. This Outlook gives an overview of its various aspects. In particular, we highlight key advances three topics: nucleophilic phosphine catalysis, organophosphorus catalysis to bypass oxide waste, and compound-mediated single electron transfer processes. We briefly summarize five additional chiral phosphoric acid Lewis base iminophosphorane super phosphonium salt phase frustrated pair catalysis. Although it is not catalytic nature, also discuss novel discoveries are emerging phosphorus(V) ligand coupling. conclude with some ideas about the future

Language: Английский

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Main Group Redox Catalysis of Organopnictogens: Vertical Periodic Trends and Emerging Opportunities in Group 15

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(4), P. 1699 - 1721

Published: Jan. 19, 2021

A growing number of organopnictogen redox catalytic methods have emerged-especially within the past 10 years-that leverage plentiful reversible two-electron chemistry Group 15. The goal this Perspective is to provide readers context understand dramatic developments in catalysis over decade with an eye toward future development. An exposition fundamental differences atomic structure and bonding pnictogens, thus molecular electronic compounds, presented establish backdrop against which reactivity-and ultimately catalysis-is framed. deep appreciation these underlying periodic principles informs understanding differing modes evokes key challenges field moving forward. We close by addressing forward-looking directions likely animate area years come. What new manifolds can be developed through creative catalyst reaction design that take advantage intrinsic reactivity pnictogens drive discoveries catalysis?

Language: Английский

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Light-promoted aromatic denitrative chlorination

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 20, 2025

Language: Английский

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An Improved P^III/P^V═O-Catalyzed Reductive C–N Coupling of Nitroaromatics and Boronic Acids by Mechanistic Differentiation of Rate- and Product-Determining Steps

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(14), P. 6786 - 6799

Published: March 16, 2020

Experimental, spectroscopic, and computational studies are reported that provide an evidence-based mechanistic description of intermolecular reductive C–N coupling nitroarenes arylboronic acids catalyzed by a redox-active main-group catalyst (1,2,2,3,4,4-hexamethylphosphetane P-oxide, i.e., 1·[O]). The central observations include the following: (1) catalytic reduction 1·[O] to PIII phosphetane 1 is kinetically fast under conditions catalysis; (2) represents resting state as observed 31P NMR spectroscopy; (3) there no long-lived nitroarene partial-reduction intermediates observable 15N (4) reaction sensitive solvent dielectric, performing best in moderately polar solvents (viz. cyclopentylmethyl ether); (5) largely insensitive with respect common hydrosilane reductants. On basis foregoing studies, new modified described expand scope for mild temperatures (T ≥ 60 °C), low loadings (≥2 mol%), innocuous terminal reductants (polymethylhydrosiloxane). DFT calculations define two-stage deoxygenation sequence coupling. initial involves rate-determining step consists (3+1) cheletropic addition between substrate 1; energy decomposition techniques highlight biphilic character this step. Although invisible, second stage implicated critical product-forming event, which postulated oxazaphosphirane intermediate diverted from arylnitrene dissociation toward heterolytic ring opening acid; resulting dipolar evolves antiperiplanar 1,2-migration organoboron residue nitrogen, displacement formation target product upon situ hydrolysis. method thus constitutes mechanistically well-defined operationally robust complement current workhorse transition-metal-based methods

Language: Английский

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Let’s Make White Phosphorus Obsolete

ACS Central Science, Journal Year: 2020, Volume and Issue: 6(6), P. 848 - 860

Published: May 18, 2020

Industrial and laboratory methods for incorporating phosphorus atoms into molecules within the framework of Green Chemistry are in their infancy. Current practice requires large inputs energy, involves toxic intermediates, generates substantial waste. Furthermore, a negligible fraction phosphorus-containing waste is recycled which turn contributes to negative environmental impacts, such as eutrophication. Methods that begin address some these drawbacks reviewed, key opportunities be realized by pursuing organophosphorus chemistry under principles highlighted. used nature, or other elements silicon, discussed model processes future chemical synthesis.

Language: Английский

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Site-specific Umpolung amidation of carboxylic acids via triplet synergistic catalysis

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: July 30, 2021

Abstract Development of catalytic amide bond-forming methods is important because they could potentially address the existing limitations classical using superstoichiometric activating reagents. In this paper, we disclose an Umpolung amidation reaction carboxylic acids with nitroarenes and nitroalkanes enabled by triplet synergistic catalysis FeI 2 , P(V)/P(III) photoredox catalysis, which avoids production byproducts from stoichiometric coupling A wide range acids, including aliphatic, aromatic alkenyl participate smoothly in such reactions, generating structurally diverse amides good yields (86 examples, up to 97% yield). This strategy opens a method challenging regioselectivity issues between nucleophilic functional groups, complements group compatibility protocols. The synthetic robustness demonstrated late-stage modification complex molecules gram-scale applications.

Language: Английский

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Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(62), P. 15277 - 15326

Published: Sept. 9, 2021

Abstract This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications title compounds design boron‐containing drugs are surveyed, with special emphasis on α‐amino derivatives. A general overview as modern tools to construct C(sp 3 )−C )‐heteroatom bonds is given, including developments Suzuki‐Miyaura Chan‐Lam cross‐couplings, single‐electron‐transfer processes metallo‐ organocatalytic photoredox reactions, transformations boron “ate” complexes. Finally, an attempt summarize current state art synthesis trifluoroborates made, a brief mention “classical” methods (transmetallation organolithium/magnesium reagents species, anti‐Markovnikov hydroboration alkenes, modification alkenyl compounds) focus methodologies (boronation alkyl (pseudo)halides, derivatives carboxylic alcohols, primary amines, boronative C−H activation, novel approaches alkene hydroboration, 1,2‐metallate‐type rearrangements).

Language: Английский

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Tandem C/N-Difunctionalization of Nitroarenes: Reductive Amination and Annulation by a Ring Expansion/Contraction Sequence

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 145(1), P. 41 - 46

Published: Dec. 23, 2022

A synthetic method for the reductive transformation of nitroarenes into ortho-aminated and -annulated products is reported. The operates via exhaustive deoxygenation by an organophosphorus catalyst a mild terminal reductant to access aryl nitrenes, which after ring expansion, are trapped amine nucleophiles give dearomatized 2-amino-3H-azepines. Treatment these ring-expanded intermediates with acyl electrophiles triggers 6π electrocyclization extrude nitrogen atom restore aromaticity phenyl ring, delivers C–H functionalization 2-aminoanilide benzimidazole products.

Language: Английский

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Nitroarenes and nitroalkenes as potential amino sources for the synthesis of N-heterocycles

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(11), P. 2254 - 2271

Published: Jan. 1, 2023

Nitro-compounds are one of the cheapest and most readily available materials, commonly used as versatile building blocks. Herein, progress in construction N-heterocycles using nitroarenes nitroalkenes is summarized by classification heterocyclic types.

Language: Английский

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

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

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