Enantioselective Sulfonation of Enones with Sulfinates by Thiourea/Tertiary-Amine Catalysis DOI
Guangxun Li, Jinzhong Zhao,

Si-fan Wang

et al.

Synlett, Journal Year: 2023, Volume and Issue: 35(12), P. 1441 - 1445

Published: Oct. 31, 2023

Abstract Chiral γ-keto sulfones are significant structures in both organic synthesis and pharmaceutical chemistry. Although there many choices for obtaining racemic forms, only a few enantioselective methods have been reported. We developed simple way chiral moderate yields enantiomeric ratios. Readily available sulfinates were directly used as substrates that could be converted into sulfinic acids by treatment with boric acid. The bifunctional catalyst forms ion pair the acid controls enantioselectivity of sulfonation through hydrogen bonding.

Language: Английский

Photochemical Halogen-Bonding Promoted Synthesis of Vinyl Sulfones via Vinyl and Sulfonyl Radicals DOI

Zhou Jiang,

Ke You,

Haibo Wu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(3), P. 636 - 641

Published: Jan. 10, 2024

A photochemical halogen-bonding-assisted synthesis of vinyl sulfones via radical–radical cross-coupling bromines and sodium sulfinates is developed. This methodology offers a facile efficient approach to various with excellent functional group tolerance under metal-, photocatalyst-, base-, oxidant-free conditions. The reaction also applicable for the late-stage functionalization drug molecules hectogram scale. Moreover, instead sulfites being prepared, these reactions could be conducted using sulfonyl chlorides in one-pot method.

Language: Английский

Citations

11
Nickel-Catalyzed Reaction between Vinyl Azides and an Alkyl Sulfonyl Radical Generated from DMSO: Rapid Access to β-Keto Sulfones DOI
Wenhui Yang, Yu Zhou, Ying Tong

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(12), P. 5046 - 5051

Published: March 14, 2024

A sustainable method for the construction of valuable β-keto sulfones lies in reaction between vinyl azides and alkyl sulfonyl radical generated from low-cost comparatively steady bulk chemical dimethyl sulfoxide (DMSO) that has been developed. This strategy features mild economical conditions using inexpensive NiCl2 as catalyst H2O2 green oxidant. The conversion occurs through a sequence ordered processes consisting addition, denitrogen, hydrogen abstraction, hydrolysis. Mechanistic studies indicate sulfinic acid produced DMSO plays an essential role reduction Ni(III). sensitivity assessment gram-scale experiments proceed smoothly to demonstrate robustness practicality this protocol.

Language: Английский

Citations

11
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

9
Hydrosulfonylation of Alkynes for Stereodivergent Synthesis of Vinyl Sulfones: Synthetic Strategy and Mechanistic Insights DOI

K P Sujith,

Steiny Russelisaac Premakumari,

Kyung‐Bin Cho

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14816 - 14828

Published: May 16, 2024

Direct synthesis of thermodynamically less favorable (Z)-vinyl sulfones presents a notable challenge in organic synthesis. In addition, the development stereodivergent for (E)- and is crucial but remains elusive. this study, we present hydrosulfonylation aryl-substituted alkynes, achieving by leveraging both thermodynamic kinetic controls. Notably, challenging was achieved through kinetically controlled process without need catalyst. To synthesize (E)-vinyl sulfones, unconventional visible light-mediated isomerization employed as means facilitating transition to favored form. The study encompasses comprehensive experimental computational investigation, which provides valuable insights into reaction mechanism. This investigation reveals two plausible pathways: novel double spin-flip mechanism hydrogen atom transfer presence eosin Y. not only advances our understanding mechanisms beyond conventional energy-transfer routes also offers robust switchable strategy synthesizing thereby providing versatile avenue creation compounds fields medicinal chemistry.

Language: Английский

Citations

4
Radical-mediated sulfonylation relay of alkyl alkynes/alkenes and electron-deficient alkenes to access vinyl and alkyl sulfones DOI
Jinhui Liu,

Fang Long,

Qing Li

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A radical-mediated sulfonylation relay of alkyl alkynes/alkenes with electron-deficient alkenes using Na 2 S O 4 as a linker is developed to synthesize highly selective ( Z )-vinyl and sulfones under metal-free catalyzed system.

Language: Английский

Citations

0
Diversity Synthesis Using Glutarimides as Rhodium Carbene Precursors in Enantioselective C–H Functionalization and Cyclopropanation DOI Creative Commons
William F. Tracy,

Jack C. Sharland,

Duc Ly

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Cereblon E3 ligase modulatory drugs (CELMoDs) can be used to target proteins and mark them for proteasomal degradation by recruiting cereblon (CRBN), the substrate receptor of CRL4CRBN ubiquitin complex. Modifications stereochemistry regiochemistry distal functionality on CELMoDs have been shown large effects activity selectivity; however, methods allowing rapid selective introduction enantioenriched moieties are rare. Herein, we report that classical CRBN-binding glutarimide cores successfully derivatized aryl diazoacetates. These diazo derivatives, when in presence a dirhodium catalyst, undergo high-yielding highly enantioselective C–H functionalization hydrocarbons cyclopropanation styrene. products create not only molecular glue degrader-like compounds but also intermediates elaborated into effective bifunctional ligand-directed degraders. Our findings highlight both effectiveness catalysis drug discovery context new method preparing diverse stereoenriched glutarimide-containing compounds.

Language: Английский

Citations

0
Direct Photoactivation of Sulfinic Acids to Access Hydrosulfonylation and Arylsulfonylation of Alkenes DOI
Yuxing Zhang,

Xi‐Rui Xia,

Siyu Guo

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

Simple and atom-economical hydrosulfonylation arylsulfonylation of alkenes have been developed using sulfinic acid as both the sulfonyl group source hydrogen atom donor under light irradiation. These reactions feature catalyst-, oxidant-, additive-free conditions, offering a highly practical approach for synthesis diversely functionalized sulfones. Preliminary mechanistic studies indicate that these proceed via photoactivation to generate radical, followed by radical chain process.

Language: Английский

Citations

0
Regio- and stereoselective manganese-catalyzed hydrosulfonylation of alkynes: facile access to Z-vinyl sulfones DOI
Jian Han, Lili Zeng, Ronghui Huang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(20), P. 5164 - 5170

Published: Jan. 1, 2023

We have reported a concise and complementary approach for the synthesis of high-selectivity ( Z )-vinyl sulfones via ligand-tuned metalloradical reactivity strategy.

Language: Английский

Citations

9
Catalyst‐Free Visible Light‐Driven Hydrosulfonylation of Alkenes and Alkynes with Sulfonyl Chlorides in Water DOI

Xi‐Rui Xia,

Juan Du, Yuxing Zhang

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: June 8, 2024

Abstract A convenient and sustainable method for synthesizing sulfonyl‐containing compounds through a catalyst‐free aqueous‐phase hydrosulfonylation of alkenes alkynes with sulfonyl chlorides under visible light irradiation is presented. Unactivated alkenes, electron‐deficient alkyl aryl can be hydrosulfonylated various at room temperature excellent yields geometric selectivities by using tris(trimethylsilyl)silane as hydrogen atom donor silyl radical precursor to activate chlorides. Mechanistic studies revealed that the photolysis in aqueous solution produce crucial success this reaction.

Language: Английский

Citations

3
Access to β‐Lactam Sulfonamides from Sulfamoyl Chlorides via Photoredox Catalyzed C−S Bond Formation DOI
Nejc Petek, Helena Brodnik, Uroš Grošelj

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(15), P. 3310 - 3315

Published: June 13, 2024

Abstract Sulfonyl chlorides are a synthetically attractive source of sulfonyl radicals in photoredox catalysis and useful precursors the synthesis sulfones. Sulfamoyl chlorides, on other hand, remain poorly represented despite their similar potential. In this study, N ‐chlorosulfonylated β‐lactams were prepared from readily available utilized an atom transfer radical addition (ATRA) reaction with variety olefins, producing β‐lactam sulfonamides 49–95% yields. β‐Lactams fused to dihydro‐1,2‐thiazine ring which closely resemble carbacephems, widely used class antibiotics, also synthesized by intra‐molecular ATRA reaction. This methodology enables preparation sulfonamides, compounds that great interest pharmacology.

Language: Английский

Citations

3