Synthesis of 2-Aryl-2<i>H</i>-benzotrizoles from Azobenzenes and <i>N</i>-Sulfonyl Azides through Sequential Rhodium-Catalyzed Amidation and Oxidation in One Pot

Ryu, Taekyu; Min, Jiae; Choi, Wonseok; Jeon, Woo Hyung; Lee, Phil Ho

doi:10.1021/ol501250t

Cited by 109 publications

(28 citation statements)

References 42 publications

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“…Glorius demonstrated the Rh(III)‐catalyzed cyclative capture approach leading to diverse 1‐aminoindolines . Moreover, Lee and Patel independently reported the facile synthesis of benzotriazoles from azobenzenes and organic azides through the Rh(III)‐ or Pd(II)‐catalyzed amination and cyclization reactions . Recently, Lee and our group described the construction of highly substituted cinnolinones derived from azobenzenes and α‐diazo esters under Rh(III) catalysis.…”

Section: Methodsmentioning

confidence: 99%

One‐pot Synthesis of Oxindoles through C−H Alkylation and Intramolecular Cyclization of Azobenzenes with Internal Olefins

Han

Mishra

et al. 2017

Adv Synth Catal

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The rhodium(III)-catalyzed site-selective CÀH alkylation of azobenzenes and internal olefins, such as maleimides, maleates and fumarates, followed by reductive intramolecular cyclization is described. A cationic rhodium catalyst in the presence of acetic acid additive in dichloroethane solvent was found to be the optimal catalytic system for the construction of ortho-alkylated azobenzenes, which smoothly underwent the intramolecular cyclization leading to the formation of C3-functionalized oxindoles in the presence of zinc powder and acetic acid. The formed oxindole scaffold could be an important asset towards the development of novel bioactive compounds.

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Section: Methodsmentioning

confidence: 99%

One‐pot Synthesis of Oxindoles through C−H Alkylation and Intramolecular Cyclization of Azobenzenes with Internal Olefins

Han

Mishra

et al. 2017

Adv Synth Catal

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“…CCDC 1575834 (3), 1443595 (12), 1575835 (13), 1575836 (14a), 1575837 (15) and 1575838 (41) contain the crystallographic data of the complexes shown in the paper; CCDC 1575459 (4), 1575460 (8) and 1575461 (17) contain the crystallographic data of the complexes shown below (SI only): bis(4-methoxyphenyl)diazomethane (5a), 3 bis(4-(dimethylamino)phenyl)diazomethane (5b), 4 methyl 2-diazo-2-(4-methoxyphenyl)acetate (6a), 5 methyl 2-diazo-2-phenylacetate (6b), 5 methyl 4-(1-diazo-2-ethoxy-2-oxoethyl)benzoate (6c), 6 9-diazo-9H-fluorene, 7 (Z)-1,2-diphenyldiazene (Z-16), 8 (E)-1,2bis(4-methoxyphenyl)diazene, 9 (E)-1,2-bis(4-fluorophenyl)diazene, 9 (E)-1,2-bis(4-(trifluoromethyl)phenyl)diazene, 10 (E)-1,2-bis(3,5-dimethylphenyl)diazene, 9,11 (E)-1,2-di-p-tolyldiazene, 9 dioctyl 4,4'-(diazene-1,2-diyl)(E)-dibenzoate, 12 (E)-1,2-bis(2,6-dimethylphenyl)diazene, 13 (E)-1,2-bis(3methoxyphenyl)diazene, 9,10 (E)-1-(p-tolyl)-2-(4-(trifluoromethyl)phenyl)diazene, 14 (E)-1,2-di-o-tolyldiazene, 9 (E)-1,1'-(diazene-1,2-diylbis(3,1-phenylene))bis(ethan-1-one), 9,15 (E)-1,2-bis(4-azidophenyl)diazene 16 . matched the previously reported values.…”

Section: Additional Crystallographic Informationmentioning

confidence: 99%

Structure and Reactivity of Half-Sandwich Rh(+3) and Ir(+3) Carbene Complexes. Catalytic Metathesis of Azobenzene Derivatives

et al. 2018

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Traditional rhodium carbene chemistry relies on the controlled decomposition of diazo derivatives with [Rh(OAc)] or related dinuclear Rh(+2) complexes, whereas the use of other rhodium sources is much less developed. It is now shown that half-sandwich carbene species derived from [Cp*MX] (M = Rh, Ir; X = Cl, Br, I, Cp* = pentamethylcyclopentadienyl) also exhibit favorable application profiles. Interestingly, the anionic ligand X proved to be a critical determinant of reactivity in the case of cyclopropanation, epoxide formation and the previously unknown catalytic metathesis of azobenzene derivatives, whereas the nature of X does not play any significant role in -OH insertion reactions. This perplexing disparity can be explained on the basis of spectral and crystallographic data of a representative set of carbene complexes of this type, which could be isolated despite their pronounced electrophilicity. Specifically, the donor/acceptor carbene 10a derived from ArC(═N)COOMe and [Cp*RhCl] undergoes spontaneous 1,2-migratory insertion of the emerging carbene unit into the Rh-Cl bond with formation of the C-metalated rhodium enolate 11. In contrast, the analogous complexes 10b,c derived from [Cp*RhX] (X = Br, I) as well as the iridium species 13 and 14 derived from [Cp*IrCl] are sufficiently stable and allow true carbene reactivity to be harnessed. These complexes are competent intermediates for the catalytic metathesis of azobenzene derivatives, which provides access to α-imino esters that would be difficult to make otherwise. Rather than involving metal nitrenes, the reaction proceeds via aza-ylides that evolve into diaziridines; a metastable compound of this type has been fully characterized.

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“…Xu, Jia, and Lee et al. independently developed the rhodium‐catalyzed direct ortho ‐amidation of azobenzenes with organoazides (Scheme ).…”

Section: Transition‐metal‐catalyzed Direct C−h Amidation and Aminatimentioning

confidence: 99%

Directing‐Group‐Assisted Transition‐Metal‐Catalyzed Direct Intermolecular C−H Amidation and Amination of Arenes

et al. 2016

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This review focuses on the most recent advances in the field of transition‐metal‐catalyzed direct intermolecular C−H amidation and amination of arenes. The manuscript is divided into two parts according to whether or not external oxidants are required. The first part includes the cases of simple neutral amines, amides, or sulfonamides in combination with external oxidants. The second section contains the examples of preactivated amino sources in the absence of any external oxidants. In each part, the content is classified in line with the different types of transition‐metal catalysts used, including Rh, Ru, Ir, Pd, Cu, Ni, Co, and Fe. In addition, the substrate scope and limitations as well as catalytic mechanism are discussed.

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Synthesis of 2-Aryl-2H-benzotrizoles from Azobenzenes and N-Sulfonyl Azides through Sequential Rhodium-Catalyzed Amidation and Oxidation in One Pot

Abstract: An efficient synthetic method of 2-aryl-2H-benzotriazoles from nonprefunctionalized azobenzenes and N-sulfonyl azides via sequential Rh-catalyzed amidation (C-N bond formation) and oxidation (N-N bond formation) with PhI(OAc)2 in one pot is reported.

Cited by 109 publications

References 42 publications

One‐pot Synthesis of Oxindoles through C−H Alkylation and Intramolecular Cyclization of Azobenzenes with Internal Olefins

One‐pot Synthesis of Oxindoles through C−H Alkylation and Intramolecular Cyclization of Azobenzenes with Internal Olefins

Structure and Reactivity of Half-Sandwich Rh(+3) and Ir(+3) Carbene Complexes. Catalytic Metathesis of Azobenzene Derivatives

Directing‐Group‐Assisted Transition‐Metal‐Catalyzed Direct Intermolecular C−H Amidation and Amination of Arenes

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