Photosensitized 1,2‐Sulfonylamination of Alkenes With Sulfonylamide DOI

Zhongping Chen,

Cong Huang, Zhenzhen Xie

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(43)

Published: Nov. 1, 2024

Abstract Herein, we developed a metal‐free, photosensitized strategy for difunctionalization of olefin feedstocks to access β‐amino sulphone architectures, enabled by tailor‐made, readily accessible sulfonylamide bifunctional reagent. This protocol could accommodate wide range alkenes and variety sulfonylamides, with high yields excellent regioselectivity. Given remarkably mild reaction conditions, starting materials, functional group tolerance, well‐defined regioselectivity, this approach would enable an efficient platform the assembly densely functionalized molecular scaffolds.

Language: Английский

A General Platform for Visible Light Sulfonylation Reactions Enabled by Catalytic Triarylamine EDA Complexes DOI
Juan D. Lasso, Durbis J. Castillo‐Pazos, Jan Michael Salgado

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2583 - 2592

Published: Jan. 17, 2024

Catalytic electron donor–acceptor (EDA) complexes have recently emerged as a powerful and sustainable alternative to iridium- ruthenium-based photoredox synthetic methods. Yet, these remain underexplored reliant on the use of meticulously designed acceptors that require previous installation. Herein, we report novel EDA complex employing tris(4-methoxyphenyl) amine catalytic donor for sulfonylation alkenes using inexpensive readily available sulfonyl chlorides. Applying this operationally simple, visible-light-mediated general platform, both redox-neutral net-reductive functionalization more than 60 substrates, encompassing vinylic or allylic sulfonylation, hydrosulfonylation, sulfamoylation activated unactivated alkynes.

Language: Английский

Citations

44
Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors DOI
Qiao Sun, Shaopeng Wang, Yuan Xu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1854 - 1941

Published: Jan. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Language: Английский

Citations

5
Photochemical and Atom-Economical Sulfonylimination of Alkenes with Bifunctional N-Sulfonyl Ketimine DOI
Lei Wang, Yang Yu, Li Deng

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(13), P. 2349 - 2354

Published: March 27, 2023

An organo-photocatalytic sulfonylimination of alkenes was developed by employing readily available N-sulfonyl ketimines as bifunctional reagents. This transformation, featuring prominent functional group tolerance, provides a direct and atom-economic approach for the synthesis valuable β-amino sulfone derivatives single regioisomer. In addition to terminal alkenes, internal participate in this reaction with high diastereoselectivity. N-Sulfonyl aryl or alkyl substituents were found be compatible condition. method could applied late-stage modifications drugs. Additionally, formal insertion alkene into cyclic sulfonyl imine observed, affording ring expansion product.

Language: Английский

Citations

29
Light-promoted photocatalyst-free and redox-neutral hydrosulfonylation of unactivated alkenes using sulfinic acid DOI

Yibo Song,

Cheng Li, Xueyuan Hu

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(11), P. 6578 - 6583

Published: Jan. 1, 2024

Using sulfinic acid as a sulfonyl source, we have developed light-promoted photocatalyst-free alkene hydrosulfonylation reaction without any additives.

Language: Английский

Citations

11
Photocatalytic Sulfonyl Peroxidation of Alkenes via Deamination of N-Sulfonyl Ketimines DOI
Yuting Feng, Shujun Chen, Leiyang Lv

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1920 - 1925

Published: Feb. 22, 2024

A photocatalytic three-component sulfonyl peroxidation of alkenes with N-sulfonyl ketimines and tert-butyl hydroperoxide is reported. The reaction takes place via the photoinduced EnT process, which allows efficient synthesis a variety β-peroxyl sulfones under mild conditions in absence transition metal catalyst. downstream derivatizations peroxides were also performed. Furthermore, utility this protocol was manifested by 11β-HSD1 inhibitor antiprostate cancer drug bicalutamide.

Language: Английский

Citations

8
Nucleophilic Substitution of Tertiary Sulfonamides: Construction of Sulfonate Esters DOI
Xuesong Du, Gang Lu, Tao Zhang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Under the combined action of trichloroisocyanuric acid (TCCA) and triflic (TfOH), tertiary sulfonamides are efficiently activated, leading to in situ generation electrophilic sulfonamide salts. These salts subsequently undergo nucleophilic substitution by alcohols, resulting formation sulfonate esters under mild conditions. Other advantages this method include absence transition-metal catalysts, broad substrate applicability, high functional-group tolerance.

Language: Английский

Citations

1
Multicomponent Sulfonylation of Alkenes to Access β-Substituted Arylsulfones DOI

Kai‐Yi Zhang,

Fang Long,

Chuan‐Chong Peng

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(6), P. 3772 - 3780

Published: March 6, 2023

A novel multicomponent sulfonylation of alkenes is described for the assembly various β-substituted arylsulfones using cheap and easily available K2S2O5 as a sulfur dioxide source. Of note, procedure does not need any extra oxidants metal catalysts exhibits relatively wide substrate scope good functional group compatibility. Mechanistically, an initial arylsulfonyl radical formed involving insertion with aryl diazonium salt, followed by alkoxyarylsulfonylation or hydroxysulfonylation alkenes.

Language: Английский

Citations

17
Light-mediated sulfonyl-iodination of ynamides and internal alkynes DOI
Mohana Reddy Mutra, Jing Li, Jeh‐Jeng Wang

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(43), P. 6584 - 6587

Published: Jan. 1, 2023

We synthesized tetrasubstituted olefins regioselectively and stereoselectively from ynamides internal alkynes with sulfonyl iodides under blue LEDs in few minutes. The key features are being metal-free, easy to handle, simple, broad scope, environmentally friendly. Furthermore, a gram-scale experiment was conducted, the corresponding sulfonyl-iodinated products were smoothly altered into various other products.

Language: Английский

Citations

16
EnT‐Mediated Amino‐Sulfonylation of Alkenes with Bifunctional Sulfonamides: Access to β‐Amino Sulfone Derivatives DOI

Ji‐Wei Sang,

Peiyu Du,

Dingding Xia

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(43)

Published: May 23, 2023

Abstract β ‐Amino sulfones are commonly found structural motifs in biologically active compounds. Herein, we report a direct photocatalyzed amino‐sulfonylation reaction of alkenes for the efficicient production important compounds by simple hydrolysis without need additional oxidants and reductants. In this transformation, sulfonamides worked as bifunctional reagents, simultaneously generating sulfonyl radicals N ‐centered which were added to alkene highly atom‐economical fashion with high regioselectivity diastereoselectivity. This approach showed functional group tolerance compatibility, facilitating late‐stage modification some bioactive sulfonamide molecules, thereby expanding relevant chemical space. Scaling up led an efficient green synthesis apremilast, one best‐selling pharmceuticals, demonstrating synthetic utility applied method. Moreover, mechanistic investigations suggest that energy transfer (EnT) process was operation.

Language: Английский

Citations

13
Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes DOI Creative Commons
Polyssena Renzi, Emanuele Azzi,

Sylvain Ascensio

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(10), P. 2721 - 2734

Published: Jan. 1, 2023

Can a cheap and bench stable salt catalyse the hydrosulfonylation of unactivated alkenes? Yes it does! Just mix diarylmethylium tetrafluoroborate with sulfinate salt, wait for formation adduct turn purple light on it.

Language: Английский

Citations

12