Rhodium‐Catalyzed C−H Activation/Annulation of Aryl Hydroxamates with Benzothiadiazol‐Containing Acetylenes: Access to Isoquinoline‐Bridged Donor‐Acceptor Luminophores

Gribanov, Pavel S.; Vorobyeva, Daria V.; Tokarev, Sergey D.; Petropavlovskikh, Dmitry A.; Loginov, Dmitry A.; Nefedov, Sergey E.; Dolgushin, Fedor M.; Osipov, Sergey N.

doi:10.1002/ejoc.202101572

Cited by 7 publications

(1 citation statement)

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“…The absence of photochromic properties in compounds IIo and IIIo could be rationalized as the formation of the TICT state upon excitation, in which the benzothienyl and isoquinolinium parts are arranged in perpendicular planes, thus preventing the 6π-electron photocyclization. As a continuation of our studies of the metal-catalyzed C–H activation, − we designed IIo and IIIo analogues bearing electron-donating groups in the isoquinolinium moiety to create a new channel for the CT process that would bypass the thienyl pendant groups. We used the rhodium-catalyzed reaction of aryl aldehydes and anilines with 1,2-bis(2,5-dimethylthiophen-3-yl)ethyne DTA to synthesize salts 1o–7o (Scheme ) with methyl, methoxy, and dialkylamino groups in the benzene ring of isoquinolinium and the orthogonal phenyl ring on the quaternary nitrogen.…”

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Redirecting of Charge Transfer Enables the Control of the Photoactivity of Terarylenes

et al. 2022

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Photoinduced charge transfer affects the efficiency and selectivity of photochemical reactions. Incorporation of donating groups into the isoquinolinium core allowed us to overcome the photochemical inactivity of the corresponding dithienyl-substituted terarylenes, presumably by redirecting the charge transfer within the molecule, and gave access to a new family of thermally reversible photoswitches.

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Redirecting of Charge Transfer Enables the Control of the Photoactivity of Terarylenes

et al. 2022

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Rhodium(III)‐catalyzed Construction of D‐A Type Polyheteroaromatics with Fluorinated Benzothiadiazole as a Modifiable Acceptor Block

et al. 2022

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An efficient pathway to a new family of fluorinated polyheteroaromatic D-A molecules has been developed. The method is based on the Rh(III)-catalyzed regioselective [4 + 2]-annulation of N-(pivaloyloxy)-benzamides with 4-ethynyl-5,6-difluoro-7-(p-methoxyphenyl)-2,1,3-benzothiadiazole as a key step followed by the aromatization/Suzuki coupling sequence to furnish the target D-A systems with modifiable acceptor block. The discovered difference in reactivity between ArB(OH) 2 and ArBPin allows performing a divergent modification of BTD acceptor block by the manipulation of aryl boronic reagents in the ortho-selective CÀ F activation of the fluorinated BTD moiety under Suzuki reaction conditions to furnish new D 1 -π-A-D 2 systems in good yields. Such stepby-step modification of the acceptor block has been achieved by Pd-catalyzed CÀ F bond activation under isoquinoline ring assistance for the first time.

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Synthesis of Isoquinoline‐Containing 5,6‐Dicyano‐2,1,3‐Benzothiadiazoles: Unusual Heterocyclization into Dibenzo‐1,6‐Naphthyridine Framework

Gribanov,

Vorobyeva,

Loginov

et al. 2024

Asian J Org Chem

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An efficient access to novel families of cyano‐containing polyheteroaromatic D‐A molecules with extended π‐conjugation, including dibenzo[c,h][1,6]naphthyridine derivatives, has been elaborated. The synthetic strategy is based on the sequence of metal‐catalyzed annulation and cross‐coupling reactions starting from available 4‐ethynyl‐5,6‐difluoro‐7‐(p‐methoxyphenyl)‐2,1,3‐benzothiadiazole to get a new series of isoquinoline‐linked BTD‐based D‐A compounds, which further undergo a selective cyanation to afford the corresponding mono‐CN‐ or di‐CN‐BTD derivatives depending on the reaction conditions. In course of the investigation of cyanation process, a new type of intramolecular heterocyclization included the transformation of the benzothiadiazole core into hardly accessible dibenzo[c,h][1,6]naphthyridine framework has been unexpectedly discovered. The protocols developed tolerate a wide range of donor blocks such as diphenylamine, carbazole, dibenzoazepine and dihydroacridine.

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Rhodium‐Catalyzed C−H Activation/Annulation of Aryl Hydroxamates with Benzothiadiazol‐Containing Acetylenes: Access to Isoquinoline‐Bridged Donor‐Acceptor Luminophores

Cited by 7 publications

References 100 publications

Redirecting of Charge Transfer Enables the Control of the Photoactivity of Terarylenes

Redirecting of Charge Transfer Enables the Control of the Photoactivity of Terarylenes

Rhodium(III)‐catalyzed Construction of D‐A Type Polyheteroaromatics with Fluorinated Benzothiadiazole as a Modifiable Acceptor Block

Synthesis of Isoquinoline‐Containing 5,6‐Dicyano‐2,1,3‐Benzothiadiazoles: Unusual Heterocyclization into Dibenzo‐1,6‐Naphthyridine Framework

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