Copper mediated C–H amination with oximes: en route to primary anilines

Xu, Li; Wang, Xing; Ma, Biao; Yin, Mingxing; Lin, Haixia; Dai, Hui‐Xiong; Yu, Jin‐Quan

doi:10.1039/c8sc01256c

Cited by 54 publications

(14 citation statements)

References 56 publications

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“…Cu, Pd0, PdII, PdIV, Ru and Ir were the famous metal catalysis. This metal catalysis used in the C-H bond activation [50][51][52]. The oxidation of C-H bond was used Cu (II) -catalyzed under air O2 condition.…”

Section: C-h Bond Oxidationmentioning

confidence: 99%

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Review for metal and organocatalysis of heterocyclic C-H functionalization

El‐Sayed¹,

Khaireldin²,

Elhefny³

2021

World J. Adv. Res. Rev.

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Over the last few decades, signiﬁcant efforts have been put forth towards the C−H bond group functionalization by transition-metalcatalysis and organocatalysis. Several efficient strategies to convert C-H bond to other groups C-C, C-N, C-O bonds have been implemented. The most attractive C-H bond functionalization was the C-H heterocyclic compounds activation that is practical method in organic synthesis. The new C–C, C–N and C–O bond as formed from the C-H bond activation by two diverse ways metal catalysis and/or organocatalysis. The most important is the synthesis of new bioactive heterocyclic compounds by easy and less expensive materials. In this review, we will cover most of the syntheses of heterocyclic derivatives by the functionalization of C-H bond in metal and organocatalytic reagents.

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Section: C-h Bond Oxidationmentioning

confidence: 99%

“…The activation of C-H bond using Cu (OAc)2 in presence of H2O and O2 could be direct oxidation of aryl C-H bond 6 which direct into ortho-position 7. Furthermore, the initial use of other copper sources, CuX2, or a combination of Cu (OAc)2 and nucleophilic anions could be equally effective [50][51][52]. (Scheme 2)…”

Section: C-h Bond Oxidationmentioning

confidence: 99%

Review for metal and organocatalysis of heterocyclic C-H functionalization

El‐Sayed¹,

Khaireldin²,

Elhefny³

2021

World J. Adv. Res. Rev.

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“…Considering the possible formation of the imine intermediate during the reaction path, we assumed that the protonolysis rather than that trigged by intramolecular nucleophiles of imine probably led to the formation of primary amine products. 13 Thus, we turned our attention to other versatile DGs and to our delight, the preliminary examination showed that the Rh( iii )-catalysed C–H coupling of 1-(pyrimidin-2-yl)indoline 4 with isoxazolone 2a occurred smoothly under the modified reaction conditions, resulting in the synthesis of the C 7 -NH 2 product 5 albeit with a relatively low yield (Scheme 3c). This result further confirmed the existence of the imine intermediate and illustrated its potential for constructing primary amines via TM-catalysed C–H coupling with isoxazolone CPs.…”

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confidence: 99%

Rh(iii)-Catalysed cascade C–H imidization/cyclization ofN-methoxybenzamides with isoxazolones for the assembly of dihydroquinazolin-4(1H)-one derivatives

Zhong

Lin

et al. 2022

Org. Chem. Front.

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“…Although copper-catalyzed electrophilic amination using organometallic reagents has been well-explored, electrophilic C–H amination by a copper catalyst is limited to the electron-deficient systems in nondirected fashion . A copper-mediated electrophilic C–H amination with oximes to primary amines was reported by the Yu group . To the best of our knowledge, copper-catalyzed directed electrophilic C–H amination has not been reported.…”

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confidence: 99%

Copper-Catalyzed Electrophilic Ortho C(sp²)–H Amination of Aryl Amines: Dramatic Reactivity of Bicyclic System

et al. 2019

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A practical copper-catalyzed, 2-picolinamidedirected ortho C−H amination of anilines with benzoylprotected hydroxylamines has been disclosed that proceeds smoothly without any external stoichiometric oxidant or additives. Remarkably, besides anilines, bicyclic naphthyl or heterocyclic amines furnished amination products with fiveand six-membered cyclic and acyclic amines at the ortho position selectively. This electrophilic C−H amination also proceeds smoothly in water under slightly modified reaction conditions.E fficient construction of C−N bonds represents one of the mainstays of research in organic synthesis over the last decades, because of the exponential use of nitrogen-containing molecules in pharmaceutical, medicinal, and materials science. 1 Following the pioneer works of Buchwald and Hartwig regarding palladium-catalyzed C−N bond formation from aryl halides and amines, 2 an impressive array of Earthabundant, inexpensive copper-catalyzed C−N coupling reactions have been explored. 3 A mechanistically distinct coppercatalyzed/mediated oxidative C−N coupling using organometallic reagents has also been developed under mild conditions. 4 A paradigm shift from transition-metal-catalyzed cross-coupling with organometallic reagents to direct C−H amination strategy has been observed in the last decades. In this vein, the research groups of Yu and Chatani independently reported copper-mediated C−H amination of 2-arylpyridines. 5 Remarkably, the Daugulis group expanded the scope of C−H amination using removable, bidentate directing groups. 6 Recently, the Chang group also reported copper-mediated C−H amination with aqueous ammonia. 7 2-Aminoanilide moiety is ubiquitously found in drug candidates for the treatment of cancer, Alzheimer's disease, wet age-related macular degeneration (wet AMD), and infectious diseases. 8 In 2014, the research groups of Rodri ́guez and Chen independently reported copper-catalyzed, 2picolinamide-directed ortho C−H amination of aniline. 9 However, stoichiometric amount of expensive PhI(OAc) 2 was used as an oxidant, which generates PhI as a byproduct. More recently, an electrochemical synthesis of C−H amination of the same substrate was reported by the Mei group, using tetrabutylammonium iodide (TBAI) as a redox mediator. 10 However, all these protocols are limited to the six-membered cyclic amines only. Acyclic amines, pyrrolidine (<5% yield),

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Copper mediated C–H amination with oximes: en route to primary anilines

Abstract: Here we report an efficient Cu(i)-mediated C–H amination reaction with oximes as amino donors to introduce NH2 groups directly.

Cited by 54 publications

References 56 publications

Review for metal and organocatalysis of heterocyclic C-H functionalization

Review for metal and organocatalysis of heterocyclic C-H functionalization

Rh(iii)-Catalysed cascade C–H imidization/cyclization ofN-methoxybenzamides with isoxazolones for the assembly of dihydroquinazolin-4(1H)-one derivatives

Copper-Catalyzed Electrophilic Ortho C(sp²)–H Amination of Aryl Amines: Dramatic Reactivity of Bicyclic System

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Copper mediated C–H amination with oximes: en route to primary anilines

Abstract: Here we report an efficient Cu(i)-mediated C–H amination reaction with oximes as amino donors to introduce NH2 groups directly.

Cited by 54 publications

References 56 publications

Review for metal and organocatalysis of heterocyclic C-H functionalization

Review for metal and organocatalysis of heterocyclic C-H functionalization

Rh(iii)-Catalysed cascade C–H imidization/cyclization ofN-methoxybenzamides with isoxazolones for the assembly of dihydroquinazolin-4(1H)-one derivatives

Copper-Catalyzed Electrophilic Ortho C(sp2)–H Amination of Aryl Amines: Dramatic Reactivity of Bicyclic System

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Copper-Catalyzed Electrophilic Ortho C(sp²)–H Amination of Aryl Amines: Dramatic Reactivity of Bicyclic System