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

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(30)

Опубликована: Май 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.

Язык: 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

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(30)

Опубликована: Май 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.

Язык: Английский

Процитировано

5
Palladium-Catalyzed Hiyama-Type Coupling of Thianthrenium and Phenoxathiinium Salts DOI

Zhiwei Cao,

J. Zhang,

Jintao Wang

и другие.

Organic Letters, Год журнала: 2024, Номер 26(31), С. 6681 - 6686

Опубликована: Июль 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.

Язык: Английский

Процитировано

4
Palladium-Catalyzed Oxidative Cycloaddition of 1-Indanones and Internal Aryl Alkynes toward Benzo[c]fluorenone Derivatives DOI
Xu Zhang,

Tongtong Ni,

Mengfan Chang

и другие.

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

Процитировано

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

и другие.

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 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.

Язык: Английский

Процитировано

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

Jia-Hui Song,

Luyao Ding

и другие.

Organic Letters, Год журнала: 2024, Номер 26(27), С. 5770 - 5775

Опубликована: Июнь 28, 2024

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

Язык: Английский

Процитировано

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

Chem, Год журнала: 2024, Номер 10(9), С. 2651 - 2665

Опубликована: Июль 29, 2024

Язык: Английский

Процитировано

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

Manojkumar Janni,

Annaram Thirupathi,

Subhashini V Subramanian

и другие.

Synthesis, Год журнала: 2024, Номер unknown

Опубликована: Июль 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.

Язык: Английский

Процитировано

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

Mengfan Chang,

Tongtong Ni

и другие.

Organic Letters, Год журнала: 2024, Номер 26(31), С. 6619 - 6624

Опубликована: Июль 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.

Язык: Английский

Процитировано

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

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(30)

Опубликована: Май 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.

Язык: Английский

Процитировано

0