Catalytic and Base‐free Suzuki‐type α‐Arylation of Cyclic 1,3‐Dicarbonyls via a Cyclic Iodonium Ylide Strategy DOI

Mingxuan Liang,

Mengling He,

Zhiqing Zhong

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(17)

Published: Feb. 22, 2024

Abstract To date, it remains challenging to achieve a general and catalytic α‐arylation of cyclic 1,3‐dicarbonyls, particularly ubiquitous heteroaromatic ones. In most cases, the preparation their medically significant arylated derivatives requires multistep synthetic sequences. Herein, we introduce new, convenient strategy involving conversion 1,3‐dicarbonyls iodonium ylides ( CIY s), followed by rhodium‐catalyzed with arylboronic reagents via carbene coupling. This approach is mild, operationally simple, base‐free, biocompatible, exhibits broad substrate scope (>100 examples), especially respect various ortho ‐substituted or base‐sensitive acids. Importantly, owing excellent compatibility acids boronate esters (ArBpin, ArBneop, ArBF 3 K), this method allows late‐stage installation heterocyclic 1,3‐dicarbonyl motifs in highly complex settings. The utility transformation further demonstrated through significantly simplifying synthesis several bioactive molecules natural products.

Language: Английский

Catalytic and Base‐free Suzuki‐type α‐Arylation of Cyclic 1,3‐Dicarbonyls via a Cyclic Iodonium Ylide Strategy DOI

Mingxuan Liang,

Mengling He,

Zhiqing Zhong

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(17)

Published: Feb. 22, 2024

Abstract To date, it remains challenging to achieve a general and catalytic α‐arylation of cyclic 1,3‐dicarbonyls, particularly ubiquitous heteroaromatic ones. In most cases, the preparation their medically significant arylated derivatives requires multistep synthetic sequences. Herein, we introduce new, convenient strategy involving conversion 1,3‐dicarbonyls iodonium ylides ( CIY s), followed by rhodium‐catalyzed with arylboronic reagents via carbene coupling. This approach is mild, operationally simple, base‐free, biocompatible, exhibits broad substrate scope (>100 examples), especially respect various ortho ‐substituted or base‐sensitive acids. Importantly, owing excellent compatibility acids boronate esters (ArBpin, ArBneop, ArBF 3 K), this method allows late‐stage installation heterocyclic 1,3‐dicarbonyl motifs in highly complex settings. The utility transformation further demonstrated through significantly simplifying synthesis several bioactive molecules natural products.

Language: Английский

Citations

10
Rh-Catalyzed α-Arylation of Cyclic 1,3-Dicarbonyls with Benzocyclobutenols Enabled by a Cyclic Iodonium Ylide Strategy DOI

Borong Su,

Zhenwei Zhang, Shangkun Zhang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4383 - 4387

Published: May 14, 2024

To date, the general and catalytic α-arylation of cyclic 1,3-dicarbonyls remains elusive. We now report first Rh-catalyzed with benzocyclobutenols through a iodonium ylide strategy. Our strategy represents good solution for previously challenging sterically demanding aryl partners, which is especially appropriate structurally unique heteroaromatic 1,3-dicarbonyls. approach features mild conditions, readily available starting materials, high yields, excellent functional group-tolerance, simple operation, providing expedient access toward medically important 2-aryl (hetero)cyclic The practicality this demonstrated by gram-scale synthesis, one-pot numerous downstream transformations.

Language: Английский

Citations

5
Cu(im) 2 -derived Cu@N–C catalyst for one-pot synthesis of 2-substituted indoles via domino Sonogashira coupling-cyclization reactions DOI Creative Commons
Jianwei Xie, Zhuangzhuang Wang,

Hui‐Fang Ma

et al.

Green Chemistry Letters and Reviews, Journal Year: 2024, Volume and Issue: 17(1)

Published: Jan. 10, 2024

Cu(im)2-derived Cu@N–C(600) catalyst has been efficiently utilized for the preparation of N-tosyl(H)−2-substituted indoles through one-pot domino Sonogashira coupling-cyclization reactions between N-tosyl(acetyl)−2-iodo anilines and aryl acetylenes. The catalytic system was heterogeneous showed excellent functional group compatibility could be performed well, affording corresponding coupling products in good to yields.

Language: Английский

Citations

3
Ru(II)-Catalyzed Carboamination of Olefins with α-Carbonyl Sulfoxonium Ylides DOI
Zhenwei Zhang,

Borong Su,

Fuhong Zhong

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(8), P. 5382 - 5391

Published: April 1, 2024

The first ruthenium-catalyzed carboamination of olefins with α-carbonyl sulfoxonium ylides is reported. utilization an inexpensive ruthenium catalyst enables the concise synthesis pharmaceutically important isoindolin-1-ones, which possess both a stereogenic center and β-carbonyl side chain. This method mild, efficient, scalable allows for coupling wide range aryl-, heteroaryl-, alkenyl-, alkyl-substituted ylides. Moreover, carbonyl chain in resulting product provides good handle downstream transformations. For mechanistic studies, ruthacyle complex obtained proven to be key intermediate catalytic stoichiometric reactions.

Language: Английский

Citations

3
Recent Advances in Sequentially Pd-Catalyzed One-Pot Syntheses of Heterocycles DOI Creative Commons
Maryna N. Kornet, Thomas J. J. Müller

Molecules, Journal Year: 2024, Volume and Issue: 29(22), P. 5265 - 5265

Published: Nov. 7, 2024

Sequential Pd-catalyzed one-pot synthetic methodologies have emerged as a powerful and versatile approach in organic synthesis, enabling the construction of complex heterocyclic architectures with high efficiency, selectivity, atom economy. This review discusses key advancements multistep, sequentially processes for accessing derivatives, focusing on classic reactions like Suzuki-Miyaura, Sonogashira, Heck, hydroamination extending to specialized techniques such directed C-H activation. The concatenation these steps has advanced scope strategies. A section is dedicated exploring cooperative use palladium other metals, particularly copper, ruthenium, gold, which broadened range accessible derivatives. Highlighted applications include synthesis biologically pharmaceutically relevant compounds, tris(hetero)aryl systems, spiro-oxindoles, indole These strategies not only streamline but also align green chemistry principles by minimizing purification reducing waste energy consumption. addresses current challenges limitations methodologies, offering insights into ongoing efforts optimize reaction conditions expand applicability sequential processes.

Language: Английский

Citations

3
Design and Synthesis of Indazole–Indole Hybrid via tert-Butyl Nitrite Mediated Cascade Diazotization/Isomerization/Cyclization DOI
Abhishek Kar, Gopal Rana,

Rajkamal Sahoo

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 7295 - 7302

Published: April 25, 2024

In this report, a tert-butyl nitrite (TBN)-mediated straightforward metal-free approach has been presented for the synthesis of diverse range C-3-substituted indazole–indole hybrids using readily accessible 2-(indolin-3-ylidenemethyl)aniline derivatives. This strategy is proposed to occur via diazonium salt intermediate that capable cascade isomerization and intramolecular C–N bond formation through 5-endo-dig cyclization achieve wide variety in good yields.

Language: Английский

Citations

2
Rhodium-Catalyzed Intramolecular Cyclization for Synthesizing Thiodihydropyrans DOI
Yunxiao Wang, Ze‐Feng Xu, Jing Chen

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(33), P. 6695 - 6698

Published: Jan. 1, 2024

Addressing the challenge of constructing multi-substituted dihydropyrans, we present an efficient synthesis method for oxygen-containing heterocycles. Using thiones and metal carbenes, employed xanthate triazole to intramolecularly synthesize dihydropyran or dihydrofuran compounds. 1,2-Hydride migration was inhibited, thiodihydropyrans were obtained in excellent yields. A mechanism proceeding through a Rh-carbene intermediate is proposed dihydropyrans synthesis.

Language: Английский

Citations

1
Catalytic and Base‐free Suzuki‐type α‐Arylation of Cyclic 1,3‐Dicarbonyls via a Cyclic Iodonium Ylide Strategy DOI

Mingxuan Liang,

Mengling He,

Zhiqing Zhong

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(17)

Published: Feb. 22, 2024

Abstract To date, it remains challenging to achieve a general and catalytic α‐arylation of cyclic 1,3‐dicarbonyls, particularly ubiquitous heteroaromatic ones. In most cases, the preparation their medically significant arylated derivatives requires multistep synthetic sequences. Herein, we introduce new, convenient strategy involving conversion 1,3‐dicarbonyls iodonium ylides ( CIY s), followed by rhodium‐catalyzed with arylboronic reagents via carbene coupling. This approach is mild, operationally simple, base‐free, biocompatible, exhibits broad substrate scope (>100 examples), especially respect various ortho ‐substituted or base‐sensitive acids. Importantly, owing excellent compatibility acids boronate esters (ArBpin, ArBneop, ArBF 3 K), this method allows late‐stage installation heterocyclic 1,3‐dicarbonyl motifs in highly complex settings. The utility transformation further demonstrated through significantly simplifying synthesis several bioactive molecules natural products.

Language: Английский

Citations

0