Recent advances in the chemistry of isolable carbene analogues with group 13–15 elements

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(8), P. 3896 - 3951

Published: Jan. 1, 2024

This review provides an overview of main group carbene analogues, covering recent advancements, synthesis strategies, and the diverse reactivity elements in groups 13–15 based on their structural characteristics.

Language: Английский

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Insights into the pH effect on hydrogen electrocatalysis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

This review systematically provides various insights into the pH effect on hydrogen electrocatalysis, and thus providing a reference for future development of electrocatalysis based these insights.

Language: Английский

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Molecular-strain induced phosphinidene reactivity of a phosphanorcaradiene

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 29, 2024

Abstract Phosphanorcaradienes are an appealing class of phosphorus compounds that can serve as synthons transient phosphinidenes. However, the synthesis such species is a formidable task owing to their intrinsic high reactivity. Herein we report straightforward synthesis, characterization and reactivity studies phosphanorcaradiene, in which one benzene rings flanking fluorenyl substituents intramolecularly dearomatized through attachment atom. It facilely obtained by reduction phosphorus(III) dichloride precursor with potassium graphite. Despite being thermally robust, it acts synthetic equivalent phosphinidene. reacts trimethylphosphine isonitrile yield phosphanylidene-phosphorane 1-phospha-3-azaallene, respectively. When treated two molar equivalents azide, iminophosphane bis(imino)phosphane isolated, Moreover, capable activating ethylene alkyne afford [1 + 2] cycloaddition products, well oxidative cleavage Si–H N–H bonds secondary phosphines. All reactions proceed smoothly at room temperature without presence transition metals. The driving force for these most likely ring-constraint three-membered PC 2 ring recovery aromaticity ring.

Language: Английский

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Advancement in Synthetic Strategies of Phosphorus Heterocycles: Recent Progress from Synthesis to Emerging Class of Optoelectronic Materials

The Chemical Record, Journal Year: 2024, Volume and Issue: 24(8)

Published: Aug. 1, 2024

Organophosphorus heterocycles have long been acknowledged for their significant potential across diverse fields, including catalysis, material science, and drug development. Incorporating phosphorus functionalities into organic compounds offers a means to effectively tailor medicinal properties, augment biological responses, enhance selectivity bioavailability. The distinctive physical photoelectric characteristics of phosphorus-containing conjugated garnered considerable interest as promising materials optoelectronics. These find extensive utility in various applications such light-emitting diodes, photovoltaic cells, phosphole-based fluorophores, semiconductors.

Language: Английский

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Enantiopure P-Chiral Secondary Phosphines (P*HRR′) from the Catalytic Asymmetric Hydrogenation of P═C Bonds

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

We report the first bottleable enantiopure

Language: Английский

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Imidazolium‐dithiocarboxylate zwitterions catalysed ring‐opening additions of cyclopropenones

Advanced Synthesis & Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Abstract Imidazolium‐dithiocarboxylate zwitterions (NHC ⋅ CS 2 ), a novel organocatalyst that derived from N‐heterocyclic carbene (NHC), was used to activate cyclopropenones. Under the catalysis of 10 mol% NHC 2, range phenols, alcohols, primary and secondary amines react with cyclopropenones produce trisubstituted α , β ‐unsaturated esters amides in 46–95% yield. More than 68 products, including 7 natural product derivatives have been synthesized through this method. Mechanism study showed act as Lewis base C=C double bond trigger ring‐opening reaction. HRMS analysis indicated formation key adduct cyclopropenone. importantly, demonstrated completely different catalytic activity catalysts, latter one cannot catalyse these reactions.

Language: Английский

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Palladium-catalyzed sequential [3+2] cyclization/C-H activation of o-iodostyrenes with cyclopropenones as C2 synthons

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A novel palladium-catalyzed synthesis of diverse dihydroindeno[2,1- a ]indenes by the sequential [3+2] cyclization/C–H activation o -iodostyrenes with cyclopropenones as C2 synthons is presented.

Language: Английский

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Cobalt- or rhodium-catalyzed synthesis of 1,2-dihydrophosphete oxides via C–H activation and formal phosphoryl migration

Chemical Science, Journal Year: 2024, Volume and Issue: 15(16), P. 6012 - 6021

Published: Jan. 1, 2024

A highly stereo- and chemoselective intermolecular coupling of diverse heterocycles with dialkynylphosphine oxides has been realized

Language: Английский

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Aromative Dephosphinidenation of a Bisphosphirane‐Fused Anthracene toward E‐H (E = H, Si, N and P) Bond Activation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: Aug. 1, 2024

Abstract A bisphosphirane‐fused anthracene ( 5 ) was prepared by treatment of a sterically encumbered amino phosphorus dichloride 3 with Mg ⋅ THF =anthracene). X‐ray diffraction analysis revealed pentacyclic framework consisting two phosphirane rings fused to the in trans ‐fashion. Compound has been shown be an efficient phosphinidene synthon, readily liberating transient units for subsequent downstream bond activation via reductive elimination under mild conditions. The formal oxidative addition H 2 and E−H (E=Si, N, P) bonds liberated provided diphosphine substituted phosphines. Furthermore, transfer alkenes alkynes smoothly yielded corresponding phosphiranes phosphirenes. mechanism investigated density functional theory (DFT) calculations.

Language: Английский

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Organophosphorus Synthesis beyond P-Cl Bond: The Development of Shelf-stable Reagents for [RP] Transfer

Current Organic Chemistry, Journal Year: 2024, Volume and Issue: 28(19), P. 1483 - 1512

Published: June 26, 2024

: The direct chlorine-free incorporation of P1 units into organic molecules has very important synthetical value owing to environmental considerations and the prospect accessing unique compounds with fascinating structures useful properties. This selective survey presents a panorama phosphorus species that are synthetic equivalents free singlet phosphinidenes [R-P] highlights state-of-art [RP]-transfer reactions emphasis on synthesis molecular architectures difficult reach using traditional methods. Among stabilized phosphinidene precursors capable RP-transfer terminal transition-metal phosphinidenoid complexes, dibenzo-7λ3- phosphinobornadienes, phosphinidene-phosphoranes, inversely polarized phosphaalkenes, phosphaketenes, intramolecularly base-stabilized phosphinidenes, (cyclo)polyphosphines diphosphenes.

Language: Английский

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