Dehydrogenative [4 + 2] Annulation of 1-Indanones with Alkynes Enabled by In-Situ-Generated Nickel Hydride DOI
Xu Zhang,

Mengfan Chang,

Tongtong Ni

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6619 - 6624

Published: July 29, 2024

A practical and effective nickel-catalyzed dehydrogenative [4 + 2] annulation of 1-indanones with alkynes was reported. In this protocol, desaturation nickel hydride catalyzed coupling were first incorporated. cyclopentadiene-type species generated in situ via β-H elimination, they subsequently reacted a wide variety to afford various benzo[a]fluorenone derivatives good yields regioselectivity.

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

6
Palladium-Catalyzed Hiyama-Type Coupling of Thianthrenium and Phenoxathiinium Salts DOI

Zhiwei Cao,

J. Zhang,

Jintao Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6681 - 6686

Published: July 26, 2024

Here, we demonstrate palladium-catalyzed Hiyama-type cross-coupling reactions of aryl thianthrenium or phenoxathiinium salts. By employing stable and inexpensive organosilanes, the arylation, alkenylation, alkynylation were realized in high efficiency using commercially available Pd(tBu3P)2 as catalyst, thus providing a reliable method for preparation biaryls, styrenes, acetylenes with broad functional group tolerance under mild conditions. Given accessibility salts from simple arenes remarkable regioselective fashion, this protocol also provides an attractive approach late-stage modification complex bioactive scaffolds.

Language: Английский

Citations

6
Palladium-Catalyzed Oxidative Cycloaddition of 1-Indanones and Internal Aryl Alkynes toward Benzo[c]fluorenone Derivatives DOI
Xu Zhang,

Tongtong Ni,

Mengfan Chang

et al.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

An efficient palladium-catalyzed dehydrogenative [4+2] annulation of 1-indanones with alkynes results in the generation diverse benzo[ c ]fluorenone derivatives satisfactory yields and regioselectivity.

Language: Английский

Citations

0
La(OTf)3-Catalyzed Benzannulation of 2-Arylidene-1H-indene-1,3(2H)-diones with Enamino Esters: Direct Access to Functionalized Fluorenone Derivatives DOI
Xuequan Wang, Dan Yue,

Changhui Yang

et al.

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

Published: March 7, 2025

An attractive method for the preparation of functional fluorenone derivatives has been developed via La(OTf)3-catalyzed benzannulation 2-arylidene-1H-indene-1,3(2H)-diones with enamino esters. The reaction involves Michael addition, intramolecular cyclization, dehydration, and aromatization in a one-step process affords wide range moderate to good yields. Moreover, this protocol provides several advantages, including broad substrate scope, readily available materials, high atom economy, applicability large-scale synthesis.

Language: Английский

Citations

0
Synthesis of 3‐Hydroxyfluorenones Based on the Cascade Reaction of Aryl Enaminones with Benzyl Substituted Cyclopropanols DOI

Xueying Yang,

Yuanshuang Xu,

Shasha Ye

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: June 4, 2025

Comprehensive Summary Presented herein is a novel synthesis of 3‐hydroxyfluorenones through the cascade reaction aryl enaminones with benzyl substituted cyclopropanols. The formation product initiated by introduction an enone moiety onto enaminone cyclopropanol as homoenolate precursor C−H bond activation, followed intramolecular enamine Michael addition, enol amine elimination and aromatization‐driven oxidative dehydrogenation. To our knowledge, this should be first example for specific 3‐hydroxyfluorenone derivatives via simultaneous both indenone phenol scaffolds C−H/C−C/C−N activation three C−C formation. In general, newly developed protocol features easily accessible substrates, synthetically pharmaceutically valuable products, unique pathway, good compatibility various functional groups ready scalability.

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

3
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

1
Palladium-Catalyzed Domino Heteroarylation of Thioamides: A Simple Route to Benzothieno[2,3-b]quinolones DOI

Manojkumar Janni,

Annaram Thirupathi,

Subhashini V Subramanian

et al.

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

Published: July 4, 2024

Abstract Domino reactions are essential for advancing organic synthesis. This study introduces novel thioamide-based precursors a palladium-catalyzed selective domino heteroarylation process. The method efficiently produces benzothieno[2,3-b]quinolones with yields ranging from moderate to very good. By employing aryl chlorides, the efficiency of hetero-annulation process is comparable that bromides. Executing one-pot, two-step reaction also delivered single product high selectivity. strategy involved fine-tuning substituent reactivity, utilizing electron-rich arenes, and forming metallocycles nucleophilic sulfur, consistently yielding product. proposed mechanism corroborated by mechanistic studies.

Language: Английский

Citations

1
Dehydrogenative [4 + 2] Annulation of 1-Indanones with Alkynes Enabled by In-Situ-Generated Nickel Hydride DOI
Xu Zhang,

Mengfan Chang,

Tongtong Ni

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6619 - 6624

Published: July 29, 2024

A practical and effective nickel-catalyzed dehydrogenative [4 + 2] annulation of 1-indanones with alkynes was reported. In this protocol, desaturation nickel hydride catalyzed coupling were first incorporated. cyclopentadiene-type species generated in situ via β-H elimination, they subsequently reacted a wide variety to afford various benzo[a]fluorenone derivatives good yields regioselectivity.

Language: Английский

Citations

1