Photocatalytic Enantioselective Hydrosulfonylation of α,β‐Unsaturated Carbonyls with Sulfonyl Chlorides DOI
Shi Cao, Doyoung Kim, Wooseok Lee

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(46)

Published: Oct. 2, 2023

Abstract This research explores the enantioselective hydrosulfonylation of various α,β‐unsaturated carbonyl compounds via use visible light and redox‐active chiral Ni‐catalysis, facilitating synthesis enantioenriched α‐chiral sulfones with remarkable enantioselectivity (exceeding 99 % ee). A significant challenge entails enhancing reactivity between metal‐coordinated moderate electrophilic sulfonyl radicals, aiming to minimize background reactions. The success our approach stems from two distinctive attributes: 1) Cl‐atom abstraction employed for radical generation chlorides, 2) single‐electron reduction produce a key enolate Ni‐complex. latter process appears enhance feasibility radical's addition electron‐rich radical. An in‐depth investigation into reaction mechanism, supported by both experimental observations theoretical analysis, offers insight intricate process. Moreover, versatility methodology is highlighted through its successful application in late‐stage functionalization complex bioactive molecules, demonstrating practicality as strategy producing sulfones.

Language: Английский

Iron-catalyzed C(sp3)–H phosphorylation via photoinduced LMCT DOI
Hongchi Liu, Kaifang Wang,

Sunfeng Ye

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 2027 - 2032

Published: Jan. 1, 2024

A redox-neutral strategy for C(sp 3 )–H phosphorylation is developed via photoinduced LMCT, where the reaction proceeds through radical addition to chlorophosphines form an R P–Cl˙ and ultimately concluded by single-electron reduction.

Language: Английский

Citations

9
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
Photocatalytic Enantioselective Hydrosulfonylation of α,β‐Unsaturated Carbonyls with Sulfonyl Chlorides DOI
Shi Cao, Doyoung Kim, Wooseok Lee

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Oct. 2, 2023

This research explores the enantioselective hydrosulfonylation of various α,β-unsaturated carbonyl compounds via use visible light and redox-active chiral Ni-catalysis, facilitating synthesis enantioenriched α-chiral sulfones with remarkable enantioselectivity (exceeding 99 % ee). A significant challenge entails enhancing reactivity between metal-coordinated moderate electrophilic sulfonyl radicals, aiming to minimize background reactions. The success our approach stems from two distinctive attributes: 1) Cl-atom abstraction employed for radical generation chlorides, 2) single-electron reduction produce a key enolate Ni-complex. latter process appears enhance feasibility radical's addition electron-rich radical. An in-depth investigation into reaction mechanism, supported by both experimental observations theoretical analysis, offers insight intricate process. Moreover, versatility methodology is highlighted through its successful application in late-stage functionalization complex bioactive molecules, demonstrating practicality as strategy producing sulfones.

Language: Английский

Citations

20
Photoinduced Direct Electron Transfer between Quinoxalin-2(1H)-ones and Alkyl Carboxylic Acids for C–H Alkylation DOI
Kaikai Niu,

Haoran Jiao,

Pan Zhou

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(50), P. 8970 - 8974

Published: Dec. 12, 2023

The progress of efficient and sustainable approaches for decarboxylative coupling reactions is synthetically appealing due to the structural diversity, lack toxicity, widespread commercial accessibility carboxylic acids. However, decarboxylation reaction still encounters challenges related utilization oxidants, catalysts, prefunctionalization conditions. We report herein a mild method that facilitates direct electron transfer between alkyl acids excited-state substrates C-H alkylation quinoxalin-2(1H)-ones without involvement any catalyst or additive.

Language: Английский

Citations

13
Synthesis of Secondary Amines via Self-Limiting Alkylation DOI Creative Commons
Pritam Roychowdhury, Saim Waheed,

Uddalak Sengupta

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4926 - 4931

Published: June 4, 2024

N-centered nucleophilicity increases upon alkylation, and thus selective partial alkylation of ammonia primary amines can be challenging: Poor selectivity overalkylation are often observed. Here we introduce N-aminopyridinium salts as surrogates for the synthesis secondary via self-limiting chemistry. Readily available N-aryl-N-aminopyridinium engage in N-alkylation situ depyridylation to afford aryl-alkyl without any products. The method overcomes classical challenges amine by accomplishing transient, highly nucleophilic pyridinium ylide intermediates applied context complex molecular scaffolds. These findings establish synthons synthetic chemistry a strategy control extent alkylation.

Language: Английский

Citations

5
Oxidant-Assisted Sulfonylation/Cyclization Cascade Synthesis of Alkylsulfonylated Oxindoles via the Insertion of SO2 DOI
Long‐Jin Zhong, Hui Chen, Xuan Shang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(8), P. 5409 - 5422

Published: April 2, 2024

An oxidant-assisted tandem sulfonylation/cyclization of electron-deficient alkenes with 4-alkyl-substituted Hantzsch esters and Na2S2O5 for the preparation 3-alkylsulfonylated oxindoles under mild conditions in absence a photocatalyst transition metal catalyst is established. The mechanism studies show that alkyl radicals, which come from cleavage C–C bond 4-substituted oxidant conditions, subsequently undergo situ insertion sulfur dioxide to generate crucial alkylsulfonyl radical intermediates. This three-component reaction provides an efficient facile route construction alkylsulfonylated avoids use highly toxic chlorides or hydrazines as sources.

Language: Английский

Citations

4
Hydrosulfonylation of Unactivated Alkenes Involving Sulfonyl Radical Generation via Photocatalytic Activation of Symmetrical Disulfones by an Energy Transfer Mimicry DOI
Dries De Vos, Ana V. Cunha,

Becky Bongsuiru Jei

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12282 - 12296

Published: Aug. 2, 2024

A visible-light-photocatalyzed hydrosulfonylation of unactivated alkenes with symmetrical disulfones using 2,4,6-triisopropylthiophenol as a hydrogen atom donor (H-D) has been developed. Generation two sulfonyl radicals from via activation visible light photocatalysis is involved. Mechanistic studies rule out that are generated disulfone an energy transfer mechanism previously found for lower oxidation state sulfur–sulfur-based reactants (i.e., thiosulfonates and disulfides). Instead, mimic process occurs. This involves photoinduced electron (PET) oxidative quenching the excited photocatalyst (*PC) disulfone, which generates radical sulfinate byproduct, followed by reduction oxidized (PC•+) this byproduct (SET) generating second (PC). The reaction can be performed in dimethyl carbonate at room temperature, features broad functional group compatibility, allows easy recycling disulfide provided 2,4,6-trisubstituted thiophenol used H-D. compared state-of-the-art green metrics.

Language: Английский

Citations

4
Traceless Nucleophile Strategy for C5‐Selective C–H Sulfonylation of Pyridines DOI Open Access
Jieun Kim, Y.G. Kim, Sungwoo Hong

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)

Published: Aug. 10, 2024

Abstract The functionalization of pyridines is crucial for the rapid construction and derivatization agrochemicals, pharmaceuticals, materials. Conventional approaches have primarily focused on ortho ‐ para ‐positions, while achieving precise meta‐selective functionalization, particularly at C5 position in substituted pyridines, remains a formidable challenge due to intrinsic electronic properties pyridines. Herein, we present new strategy meta C5‐selective C−H sulfonylation N ‐amidopyridinium salts, which employs transient enamine‐type intermediate generated through nucleophilic addition salts. This process harnesses power electron donor‐acceptor complexes, enabling high selectivity broad applicability, including complex bearing valuable sulfonyl functionalities under mild conditions without need an external photocatalyst. remarkable selectivity, combined with applicability late‐stage significantly expands toolbox pyridine unlocking access previously unattainable ‐sulfonylated

Language: Английский

Citations

4
DBU‐Promoted [3 + 2] Cyclization/Retro‐Mannich Cascade Reaction of N‐Aminoisoquinolinium and N‐Aminoquinolinium Derivatives with para‐Quinone Methides DOI
Shaohong Ma, Mingyang Chen, Zifeng Yang

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(9), P. 2003 - 2007

Published: March 12, 2024

Abstract A DBU‐promoted [3+2] cyclization/retro‐Mannich cascade reaction of N ‐aminoisoquinolinium and ‐aminoquinolinium derivatives with para ‐quinone methides has been established, employing a C=C double bond cleavage. broad range salts, are well tolerated, providing the corresponding rearrangement products. Moreover, scaled‐up reactions diverse derivatizations products were also investigated discussed.

Language: Английский

Citations

3
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