Site‐Selective Ortho/Ipso C−H Difunctionalizations of Arenes using Thianthrene as a Leaving Group DOI Creative Commons
Dorian Dupommier, Martin Vuagnat, Javid Rzayev

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(30)

Published: May 7, 2024

Abstract Site‐selective ortho/ipso C−H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4‐tetrasubstituted ones (62 examples, up 97 % yields). To ensure the excellent regioselectivity process while keeping high efficiency, an original strategy based on a “C−H thianthenation/Catellani‐type reaction” sequence was developed starting from simple arenes. Non‐prefunctionalized first regioselectively converted into corresponding thianthrenium salts. Then, palladium‐catalyzed, norbornene (NBE)‐mediated allowed synthesis ipso ‐olefinated/ ortho ‐alkylated using thianthrene as leaving group (revisited Catellani reaction). Pleasingly, commercially available (NBE) and unique catalytic system, synthetic challenges known for reaction with aryl iodides smoothly successfully tackled “thianthrenium” approach. The protocol robust (gram‐scale reaction) widely applied two‐fold functionalization various bio‐active compounds. Moreover, panel olefins alkyl halides coupling partners suitable. further incorporation other groups at (CN/alkyl/H, aryl) (alkyl, aryl, amine, thiol) positions, showcasing generality process.

Language: Английский

Site‐Selective Ortho/Ipso C−H Difunctionalizations of Arenes using Thianthrene as a Leaving Group DOI Creative Commons
Dorian Dupommier, Martin Vuagnat, Javid Rzayev

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 7, 2024

Abstract Site‐selective ortho/ipso C−H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4‐tetrasubstituted ones (62 examples, up 97 % yields). To ensure the excellent regioselectivity process while keeping high efficiency, an original strategy based on a “C−H thianthenation/Catellani‐type reaction” sequence was developed starting from simple arenes. Non‐prefunctionalized first regioselectively converted into corresponding thianthrenium salts. Then, palladium‐catalyzed, norbornene (NBE)‐mediated allowed synthesis ipso ‐olefinated/ ortho ‐alkylated using thianthrene as leaving group (revisited Catellani reaction). Pleasingly, commercially available (NBE) and unique catalytic system, synthetic challenges known for reaction with aryl iodides smoothly successfully tackled “thianthrenium” approach. The protocol robust (gram‐scale reaction) widely applied two‐fold functionalization various bio‐active compounds. Moreover, panel olefins alkyl halides coupling partners suitable. further incorporation other groups at (CN/alkyl/H, aryl) (alkyl, aryl, amine, thiol) positions, showcasing generality process.

Language: Английский

Citations

5
Pd/NBE-Catalyzed One-Pot Modular Synthesis of Polycyclic Fused δ-Lactams and Investigation of Room-Temperature Phosphorescence DOI
Chen Chen, Chang Ni,

Jia-Hui Song

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12181 - 12191

Published: July 30, 2024

The advancement of sophisticated synthetic methodologies that streamline reaction processes while enhancing molecular complexity is a perpetual necessity in the realm chemistry. Catalytic one-pot cascade play crucial role efficient construction intricate molecules with exceptional chemoselectivity. Herein, we present approach for synthesis polycyclic fused δ-lactams via sequential phosgenation, Pd/NBE-catalyzed ortho-carbamoylation/ipso-Heck-type cyclization, and C–H activation from readily available aryl halides, amines, triphosgenes. This stands out as first example situ carbamoyl chloride formation amine precursors, presenting an alternative to existing transformations involving chlorides. practical significance these showcased by 81 rapid economically favorable manner, without need intermediate purification. Moreover, were scalable compatible various natural products pharmaceuticals, further underscoring effectiveness this strategy. relatively rigid coplanar structure displayed our synthesized exhibits distinct room-temperature phosphorescence characteristics, which have been utilized anticounterfeiting high-security-level data encryption.

Language: Английский

Citations

4
Palladium-Catalyzed Site-Selective C–H Sulfonylation via Aryl Thianthrenium Salts to Access Diarylsulfones DOI
Chunjie Ni, Jinping Liu,

Xiaoxu Zhang

et al.

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

Published: Feb. 21, 2025

We presented a highly efficient palladium-catalyzed site-selective C-H sulfonylation reaction via aryl thianthrenium salts. By utilizing readily available and cost-effective arenes along with sodium sulfinates, we achieved the C(sp2)-S cross-coupling high efficiency, establishing dependable method for synthesizing diarylsulfones satisfactory yields. This exhibits excellent tolerance toward functional groups, scalability, synthesis or late-stage functionalization of bioactive molecules, making it valuable tool drug modifications.

Language: Английский

Citations

0
Pd/NBE-Catalyzed One-Pot Modular Synthesis of Tetrahydro-γ-carbolines DOI

Cuifeng Huang,

Wenlin Zhang, Ying Liu

et al.

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

Published: April 14, 2025

Tetrahydro-γ-carbolines are especially outstanding fused heterocyclic ring systems possessing significant biological activities in the central nervous system. Here, using commercially available NBE derivatives (NBEs), we report an efficient protocol for one-pot modular synthesis of 4-substituted tetrahydro-γ-carbolines via Catellani/aza-Michael addition cascade from easily 3-iodo-1-tosyl-1H-indole, aziridines and olefins. This approach exhibits a wide substrate scope, good yields, scalability, potential extension toward Mebhydroline analogues.

Language: Английский

Citations

0
Modular Synthesis of Polysubstituted α-Phosphorylated Arenes via the Catellani Strategy DOI
Chen Chen,

Jia-Hui Song,

Luyao Ding

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5770 - 5775

Published: June 28, 2024

In this paper, we described a palladium/norbornene-catalyzed

Language: Английский

Citations

3
New trends for transition metal-catalyzed ortho/ipso difunctionalizations of arenes DOI
Dorian Dupommier, Tatiana Besset

Chem, Journal Year: 2024, Volume and Issue: 10(9), P. 2651 - 2665

Published: July 29, 2024

Language: Английский

Citations

2
Palladium-Catalyzed Dual C–H Arylation/Cyclization Reaction of Iodoferrocenes with ortho-Bromobenzamides for the Construction of Arylated Isoquinolone-Fused Ferrocenes DOI
Zhiyong Li,

Jingyu Li,

Jing-Wen Fan

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 11, 2024

We reported a palladium/norbornene-catalyzed dual intermolecular C-H arylation/intramolecular cyclization reaction of iodoferrocenes with

Language: Английский

Citations

1
Site‐Selective Ortho/Ipso C−H Difunctionalizations of Arenes using Thianthrene as a Leaving Group DOI Creative Commons
Dorian Dupommier, Martin Vuagnat, Javid Rzayev

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(30)

Published: May 7, 2024

Abstract Site‐selective ortho/ipso C−H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4‐tetrasubstituted ones (62 examples, up 97 % yields). To ensure the excellent regioselectivity process while keeping high efficiency, an original strategy based on a “C−H thianthenation/Catellani‐type reaction” sequence was developed starting from simple arenes. Non‐prefunctionalized first regioselectively converted into corresponding thianthrenium salts. Then, palladium‐catalyzed, norbornene (NBE)‐mediated allowed synthesis ipso ‐olefinated/ ortho ‐alkylated using thianthrene as leaving group (revisited Catellani reaction). Pleasingly, commercially available (NBE) and unique catalytic system, synthetic challenges known for reaction with aryl iodides smoothly successfully tackled “thianthrenium” approach. The protocol robust (gram‐scale reaction) widely applied two‐fold functionalization various bio‐active compounds. Moreover, panel olefins alkyl halides coupling partners suitable. further incorporation other groups at (CN/alkyl/H, aryl) (alkyl, aryl, amine, thiol) positions, showcasing generality process.

Language: Английский

Citations

0