Electrochemical Approach for Direct C–H Phosphonylation of Unprotected Secondary Amine

Organic Letters, Год журнала: 2019, Номер 21(19), С. 7759 - 7762

Опубликована: Сен. 17, 2019

Direct α-phosphonylation of an unprotected secondary amine in a single step is practical importance to amino phophophates. However, this protocol limited due the high redox barrier amine. In paper, we report C–H phosphonylation via electrochemical approach presence catalytic carboxylate salt. This metal-free and exogenous oxidant-free method furnishes diverse target molecules with satisfactory yield under mild reaction conditions. Successful application gram-scale experiment demonstrates potential utility for further functionalization.

Язык: Английский

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Photoinduced Decarboxylative Phosphorothiolation ofN-Hydroxyphthalimide Esters

Organic Letters, Год журнала: 2021, Номер 23(17), С. 6729 - 6734

Опубликована: Авг. 19, 2021

A visible-light-induced protocol for the synthesis of phosphorothioates is developed by employing Ir-catalyzed decarboxylative phosphorothiolation N-hydroxyphthalimide esters. This novel method utilizes carboxylic acids as raw material, which stable, cheap, and commercially available. Scope studies show that this reaction has good compatibility functional groups. Notably, both steric hindrance later modification some bioactive compounds are successfully achieved.

Язык: Английский

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Access to S-Stereogenic Free Sulfoximines via Bifunctional Phosphonium Salt-Catalyzed Desymmetrization of Bisphenols

ACS Catalysis, Год журнала: 2021, Номер 11(22), С. 13902 - 13912

Опубликована: Ноя. 1, 2021

Sulfur-stereogenic sulfoximines particularly with a free N-H unit exhibit intriguing chemical and biological activities, thus have received continuous attention from chemists. However, there are currently no examples of guiding catalytic asymmetric strategies available to directly access these molecules. Herein, we disclose an efficient practical protocol for the direct enantioenrichment sulfoximines, via bifunctional phosphonium salt-catalyzed desymmetrization triggered by Atherton–Todd reaction together further extended nucleophilic acyl substitution-type reaction. A series bearing assortment aromatic groups (70 examples) tolerated in this incidentally involving minority kinetic resolution (KR). The desymmetrized products can be easily transformed into chiral sulfoxides other classes active sulfur-stereogenic compounds. Mechanistic studies provided insights pathway suggesting desymmetrization/KR synergic process, also offered support on hydrogen-bonding interactions as key elements successful stereocontrol.

Язык: Английский

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Electrochemical Oxidative Phosphorylations of Glycine Derivatives with R₂P(O)−H‐Containing Compounds via C(sp³)−H Functionalisation

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(6), С. 900 - 905

Опубликована: Фев. 20, 2023

Herein, we report the development of transition-metal-catalyst- and external-oxidant-free electrochemical cross-coupling hydrogen-evolution chemistry involving glycine amides diarylphosphine oxides. A broad range biologically active α-aminophosphonates was obtained in moderate to good yields a clean sustainable manner. Moreover, TBAB (tetrabutylammonium bromide) electrolyte recycled four times without obvious loss reaction activity. this protocol performed on gram scale under slightly modified electrolytic conditions or combination with continuous flow microreactor technology. Control experiments were used disclose possible free-radical mechanism. As service our authors readers, journal provides supporting information supplied by authors. Such materials are peer reviewed may be re-organized for online delivery, but not copy-edited typeset. Technical support issues arising from (other than missing files) should addressed Please note: The publisher is responsible content functionality any Any queries content) directed corresponding author article.

Язык: Английский

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Recent Advances in the Direct Synthesis of Sulfur‐Containing Organophosphorus Compounds via Radical Processes

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(14), С. 2280 - 2298

Опубликована: Июнь 14, 2023

Abstract Phosphonothioates, phosphinothioates and phosphorothioates are regarded as an important class of sulfur‐containing organophosphorus compounds. Because the unique P(O)S−R group, these compounds have biological activities thus been widely used in fields pharmaceuticals pesticides. In recent years, development by radical processes has attracted considerable attention chemistry. Along lines, this review, advances synthesis were systematically summarized. According to different ways generating radicals during formation process phosphonothioates, phosphorothioates, transformations can be divided into four categories: (1) Oxidant or metal‐free promoted transformation fabricate compounds; (2) Copper‐catalyzed produce (3) Photo‐induced prepare (4) Electro‐induced derive

Язык: Английский

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Metal- and oxidant-free electrochemical synthesis of sulfinic esters from thiols and alcohols

Green Chemistry, Год журнала: 2019, Номер 21(20), С. 5528 - 5531

Опубликована: Янв. 1, 2019

An eco-friendly electrochemical synthesis of sulfinic esters from thiols and alcohols under mild reaction conditions has been developed.

Язык: Английский

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Electrochemical Oxidative C−H Sulfonylation of Anilines

Asian Journal of Organic Chemistry, Год журнала: 2019, Номер 8(10), С. 1838 - 1841

Опубликована: Авг. 12, 2019

Abstract An electrochemical oxidative C−H sulfonylation of anilines without a metal catalyst and an external oxidant has been developed. Various sodium sulfinates are compatible, generating the desired products in up to 96% yield. Preliminary mechanism studies suggest that radical cross‐coupling process is involved this transformation.

Язык: Английский

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Diselenide-Mediated Catalytic Functionalization of Hydrophosphoryl Compounds

Organic Letters, Год журнала: 2020, Номер 22(15), С. 5811 - 5816

Опубликована: Июль 16, 2020

We report a diaryldiselenide catalyst for cross-dehydrogenative nucleophilic functionalization of hydrophosphoryl compounds. The proposed organocatalytic cycle closely resembles the mechanism Atherton–Todd reaction, with serving as recyclable analogue halogenating agent employed in named reaction. Phosphorus and selenium NMR studies reveal existence P–Se bond intermediate, structural analyses indicate stereospecific

Язык: Английский

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Design of Photoactive Covalent Organic Frameworks as Heterogeneous Catalyst for Preparation of Thiophosphinates from Phosphine Oxides and Thiols

Chemistry - A European Journal, Год журнала: 2022, Номер 28(26)

Опубликована: Март 14, 2022

Two new covalent organic frameworks (COFs) were synthesized from 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayl)tetraaniline and 2,5-dimethoxyterephthalaldehyde (Py-DMTA-COF) or 2',5'-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde (Py-DMTPDA-COF) under solvothermal conditions. These two COFs further facilely developed as efficient photocatalytic platforms for the synthesis of thiophosphinates. Py-DMTA-COF exhibited better activity, broad substrate applicability, excellent recycling capacity preparation thiophosphinates P(O)H compounds thiols compared to Py-DMTPDA-COF. This methodology was extended seamless gram-scale production target phosphorothioate derivatives. The results demonstrate that can provide a robust platform developing metal-free, base-free, highly efficient, reusable heterogeneous photocatalysts transformations.

Язык: Английский

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Visible light photocatalytic phosphorylation of heteroatom nucleophiles triggered by phosphorus-centered radical cations

Green Chemistry, Год журнала: 2023, Номер 25(11), С. 4528 - 4535

Опубликована: Янв. 1, 2023

A photocatalytic phosphorylation of heteroatom nucleophiles has been achieved via the direct coupling phosphorus-centered radical cations with nucleophiles.

Язык: Английский

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