Metal-Free S-Arylation of Phosphorothioate Diesters and Related Compounds with Diaryliodonium Salts

Organic Letters, Journal Year: 2023, Volume and Issue: 25(4), P. 671 - 675

Published: Jan. 20, 2023

We developed a direct metal-free S-arylation of phosphorothioate diesters using diaryliodonium salts. The method allows for the preparation under simple conditions broad range S-aryl phosphorothioates, including complex molecules (e.g., dinucleotide or TADDOL derivatives), as well other related organophosphorus compounds arylated at chalcogen. reaction proceeds with full retention stereogenic center phosphorus atom, opening convenient access to P-chiral products. mechanism was established DFT calculations.

Language: Английский

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Metal-free direct C–H phosphonation of N-heterocycles with diphenylphosphine oxides under mild conditions

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(14), P. 5721 - 5726

Published: Jan. 1, 2023

Herein, metal-free phosphonation of N-heterocycles with diphenylphosphine oxides, promoted by 1,5-diazabicyclo[5,4,0]undec-5-ene utilizing air as a green oxidant in dimethyl carbonate an eco-friendly solvent at room temperature, is presented.

Language: Английский

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Photoinduced Decarboxylative Phosphorothiolation ofN-Hydroxyphthalimide Esters

Organic Letters, Journal Year: 2021, Volume and Issue: 23(17), P. 6729 - 6734

Published: Aug. 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.

Language: Английский

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Photochemical halogen-bonding assisted carbothiophosphorylation reactions of alkenyl and 1,3-dienyl bromides

Chemical Science, Journal Year: 2023, Volume and Issue: 14(44), P. 12767 - 12773

Published: Jan. 1, 2023

Herein, we present a synthetic procedure for the facile and general preparation of novel S-alkenyl dienyl phosphoro(di)thioates first time. Extensive mechanistic investigations support that reactions rely on photochemical excitation halogen-bonding complex, formed with phosphorothioate salt an alkenyl or bromide, which light-induced fragmentation leads to formation desired products through radical-based pathway. The substrate scope is broad exhibits wide functional group tolerance in final compounds, including molecules derived from natural products, all unknown potentially interesting biological properties. Eventually, very efficient continuous flow protocol was developed upscale these reactions.

Language: Английский

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Electrochemical phosphorothiolation and 1,4-S → C phospho-Fries rearrangement: controlled access to phosphorothiolated and mercapto-phosphono substituted indolizines

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(20), P. 5198 - 5204

Published: Jan. 1, 2023

An unprecedented electrochemically regioselective C–H phosphorothiolation and S- to C-[1,4] phosphonyl migration involving indolizines, elemental sulfur, H-phosphonates in an undivided cell has been developed.

Language: Английский

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Copper-Catalyzed Multicomponent Trifluoromethylphosphorothiolation of Alkenes: Access to CF₃-Containing Alkyl Phosphorothioates

Organic Letters, Journal Year: 2021, Volume and Issue: 23(15), P. 5848 - 5852

Published: July 12, 2021

An unprecedented copper-catalyzed multicomponent radical-based reaction involving alkenes, P(O)H compounds, sulfur powder, and Togni reagent II at room temperature has been developed. A variety of highly functionalized CF3-containing S-alkyl phosphorothioates can be directly prepared from a wide range activated unactivated alkenes. Moreover, this protocol highlights its potential in the late-stage functionalization complex molecules opens up new avenue for construction C(sp3)–S–P bonds.

Language: Английский

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Copper and Photocatalytic Radical Relay Enabling Fluoroalkylphosphorothiolation of Alkenes: Modular Synthesis of Fluorine-Containing S-Alkyl Phosphorothioates and Phosphorodithioates

Organic Letters, Journal Year: 2021, Volume and Issue: 23(23), P. 9267 - 9272

Published: Nov. 15, 2021

A photoredox and copper-catalyzed fluoroalkylphosphorothiolation of activated unactivated alkenes via a radical relay mechanism is reported. By employing fluoroalkyl halides as precursors P(O)SH or P(S)SH compounds coupling partners, wide range β-monofluoroalkyl-, -difluoroalkyl-, -trifluoromethyl-, -perfluoroalkyl-substituted S-alkyl phosphorothioates phosphorodithioates can be easily constructed under mild conditions with good functional group tolerance. Furthermore, this modular reaction system successfully applied to late-stage functionalization bioactive molecules.

Language: Английский

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Photoredox and Copper‐Catalyzed Sulfonylphosphorothiolation of Alkenes toward β‐Sulfonyl Phosphorothioates

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(18), P. 3316 - 3320

Published: Aug. 20, 2022

Abstract A photoredox and copper‐catalyzed sulfonylphosphorothiolation of alkenes has been developed. With the use readily available aryl or alkyl sulfonyl chlorides as radical precursors (RO) 2 P(O)SH coupling partners, a wide range decorated β‐sulfonyl phosphorothioates could be obtained in 37–98% yields with good functional group tolerance. Importantly, this three‐component reaction can conveniently extended to late‐stage modification bioactive molecules gram‐scale synthesis. magnified image

Language: 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, Journal Year: 2022, Volume and Issue: 28(26)

Published: March 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.

Language: Английский

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

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(11), P. 4528 - 4535

Published: Jan. 1, 2023

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

Language: Английский

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