Copper‐ and Cobalt‐Catalyzed Syntheses of Thiophene‐Based Tertiary Amines

Bouarfa, Salima; Graßl, Simon; Ivanova, Maria V.; Langlais, Timothy; Bentabed‐Ababsa, Ghenia; Lassagne, Frédéric; Erb, William; Roisnel, Thierry; Dorcet, Vincent; Knöchel, Paul; Mongin, Florence

doi:10.1002/ejoc.201900276

Cited by 10 publications

(9 citation statements)

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“…In the course of a study published recently, we observed that copper-catalyzed N,N-diarylation of thienylamines is possible by using an excess of aryl iodide in the presence of 1 equivalent of activated copper and 3 equivalents of base. 58 Hence, 2-aminobenzaldehyde (1) was similarly treated by the different iodoanisoles (2 equiv) at the reflux temperature of dibutyl ether until disappearance of the starting materials. The expected 2-(diarylamino)benzaldehydes 6b-d were isolated in 14 to 63% yield, as a result of side reactions/degradation taking place in the course of the second, more difficult Narylation step (Table 2, entries 1-3, left).…”

Section: Syntheses Of Acridonesmentioning

confidence: 99%

2-Aminobenzaldehyde, a common precursor to acridines and acridones endowed with bioactivities

et al. 2020

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By starting from a common substrate, 2-aminobenzaldehyde, both acridines and acridones were prepared. The former were generated in high yields by copper-catalyzed N-arylation followed by acidmediated cyclization while the latter were obtained by double copper-catalyzed N-arylation followed by cyclization under the same reaction conditions. Moreover, acridine was subjected to deprotometalation by recourse to a lithium-zinc base and converted to the corresponding 4-iodo derivative, which was involved in copper-catalyzed couplings with pyrrolidinone and pyrazole. Finally, addition of pyrazole, indole and carbazole onto the 9 position of bare acridine was improved. While moderate biological activity was noticed in melanoma cells growth inhibition, the newly prepared compounds feature interesting photophysical properties which were evaluated in a preliminary study. moderate cytotoxic activity against liver cancer cell line WRL-68 (IC50 = 86 M). Finally, citrusinine-I is a natural acridone reported as herbicide model due to its ability to inhibit photosynthesis (Figure 1, right). 1bAcridines and acridones are traditionally prepared by using as key step copper-catalyzed C-N bond formation reactions between 2-halogenobenzoic acids and anilines. 1a,b Among other methods reported to access acridines, 2 we can cite (i) the Bernthsen synthesis in which diphenylamine and carboxylic acids are heated in the presence of zinc chloride as catalyst to furnish 9-substituted acridines, 3 (ii) palladium-catalyzed N-arylation/intramolecular Heck reaction of 2-bromostyrenes with 2chloroanilines developed by Buchwald and co-workers, 4 (iii) [4+2] annulation of 2-aminoaryl ketones with in situ formed arynes (by treating 2-(trimethylsilyl)aryl triflates with cesium fluoride) documented by Larock and co-workers to afford unsymmetrical acridines, 5 (iv) palladium-catalyzed consecutive C=C bond and C-N bond formations between 1,2-dibromobenzenes and N-tosyl hydrazones of 2aminophenyl ketones reported by Wang and co-workers, 6 (v) the appoach of Ellman and co-workers who employed aromatic azides with aromatic imines in a [3+3] annulation reaction (Rh(III)-catalyzed amination followed by intramolecular electrophilic aromatic substitution and aromatization), 7 (vi) palladium-catalyzed N-arylation/Friedel-Crafts reactions of anilines reported by Guo, Wang and coworkers from 2-formylphenyl triflates and anilines, 8 and by Xu and co-workers from 2bromobenzaldehydes, 9 both in the presence of copper salts, (vii) tandem N-arylation/Friedel-Crafts reactions of 2-aminophenones with diaryliodonium salts 10 and arylboronic acids, 11 (viii) Wang's 12 and Wu's 13 annulation-aerobic oxidative dehydrogenation and Deng's palladium-catalyzed reaction 14 of 2aminophenones with cyclohexanones, and (ix) Jiang's nitrogen/iodine exchange of diaryliodonium salts with sodium azide 15 (Scheme 1). 4Scheme 1. General ways reported in the literature to access acridines. Among a few other specific syntheses, 16 the general ways to access acridones include (i) acidinduce...

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Section: Syntheses Of Acridonesmentioning

confidence: 99%

2-Aminobenzaldehyde, a common precursor to acridines and acridones endowed with bioactivities

et al. 2020

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“…From 2018 to now, Knochel et al have reported several procedures for the coupling of O -benzoylhydroxylamines under cobalt catalysis. − The authors first reported the use of ArZnCl·Mg(OPiv) 2 ·LiCl complexes, referred as arylzinc pivalate and abbreviated “ArZn(OPiv)” in such couplings . These complexes can be obtained by transmetalation of Grignard reagents with Zn(OPiv) 2 .…”

Section: Umpolung Couplingsmentioning

confidence: 99%

“…This method was then expanded to thiophene-derived heteroarylzinc chloride reagents . These reagents were obtained by Mg insertion ( 14 ), halogen/Mg exchange ( 15 ) or deprotonation ( 16 ), followed by a transmetalation with ZnCl 2 .…”

Section: Umpolung Couplingsmentioning

confidence: 99%

N-(Hetero)arylations with Metalated (Hetero)aryls: Recent Advances in First-Row Transition-Metal-Mediated Cross-Couplings

Ribaucourt

Cossy

2020

ACS Catal.

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Transition-metal-catalyzed C(sp 2 )−N bond forming reactions represent a very active field of research in chemistry. This review outlines the recent developments of the first-row transition-metal-catalyzed non-Buchwald−Hartwig cross-couplings (i.e., not taking place between a (hetero)aryl (pseudo)halide and an amine or other nitrogen-containing derivatives). The oxidative and umpolung cross-couplings represent the two main types of transformations discussed in this review.

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“…Besides direct introduction of an amino group by a Chichibabin reaction [ 4 ], functionalization at C-4 can be achieved by a direct deprotometalation-amination reaction ( Scheme 22 ). This methodology appears complementary to access to several 4-amino substituted 1,5-naphthyridines 62a – c [ 54 ].…”

Section: Reactivity Of 15-naphthyridinesmentioning

confidence: 99%

“…Functionalization at C-4 of 1,5-naphthyridine heterocycle 2a can be achieved by a direct deprotometalation-amination reaction (vide supra, Scheme 22 ) or by an indirect amination. The latter method involves a previously deprotometalation-iodolysis substitution reaction to afford the intermediate 81 ( Scheme 29 ), which permitted the access to a variety of 4-amino substituted 1,5-naphthyridines 62 (previously prepared, vide supra, Scheme 22 ) [ 54 ].…”

Section: Reactivity Of 15-naphthyridinesmentioning

confidence: 99%

Synthetic Strategies, Reactivity and Applications of 1,5-Naphthyridines

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This review covers the synthesis and reactivity of 1,5-naphthyridine derivatives published in the last 18 years. These heterocycles present a significant importance in the field of medicinal chemistry because many of them exhibit a great variety of biological activities. First, the published strategies related to the synthesis of 1,5-naphthyridines are presented followed by the reactivity of these compounds with electrophilic or nucleophilic reagents, in oxidations, reductions, cross-coupling reactions, modification of side chains or formation of metal complexes. Finally, some properties and applications of these heterocycles studied during this period are examined.

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Copper‐ and Cobalt‐Catalyzed Syntheses of Thiophene‐Based Tertiary Amines

Cited by 10 publications

References 102 publications

2-Aminobenzaldehyde, a common precursor to acridines and acridones endowed with bioactivities

2-Aminobenzaldehyde, a common precursor to acridines and acridones endowed with bioactivities

N-(Hetero)arylations with Metalated (Hetero)aryls: Recent Advances in First-Row Transition-Metal-Mediated Cross-Couplings

Synthetic Strategies, Reactivity and Applications of 1,5-Naphthyridines

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