Cp*Co<sup>III</sup>-catalyzed formal [4+2] cycloaddition of benzamides to afford quinazolinone derivatives

Yang, Jingshu; Hu, Xin; Liu, Zijie; Li, Xueyuan; Dong, Yunhui; Li, Gang

doi:10.1039/c9cc07173c

Cited by 33 publications

(16 citation statements)

References 83 publications

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“…37 Starting from 3aw, schizocommunin (6), a fungal alkaloid that is cytotoxic against murine lymphoma cells by activating aryl hydrocarbon receptor gene battery, can be constructed by exploiting the nucleophilicity of methyl substituent. 38,39 This nucleophilicity of methyl group also allows the use of 3aw in a threestep assembly of 7, a potent promoter of p53 activity in rhabdomyosarcoma. 40,41 The methyl group can be rendered electrophilic by bromination for synthetic access to 8, an inhibitor of tubulin assembly that shows anti-proliferative activity against HT29 cell line.…”

Section: Resultsmentioning

confidence: 99%

Cobalt Homeostatic Catalysis for Coupling of Enaminones and Oxadiazolones to Quinazolinones

Fan

et al. 2022

Preprint

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Transition metal catalysis has revolutionized modern synthetic chemistry for its diverse modes of coordination reactivity. However, this versatility in reactivity is also the predominant cause of catalyst deactivation, a persisting issue that can significantly compromise its synthetic value. Homeostatic catalysis, a catalytic process that can sustain its productive catalytic cycle even when chemically disturbed, is proposed herein as an effective tactic to address the challenge. In particular, a cobalt homeostatic catalysis process has been developed for water-tolerant coupling of enaminones and oxadiazolones to quinazolinones. Dynamic covalent bonding serves as a mechanistic handle for preferred buffering of water onto enaminone and reverse exchange back by released secondary amine, thus securing reversible entry into cobalt dormant and active states for productive catalysis. Through this homeostatic catalysis mode, a broad structural scope has been achieved for quinazolinones, enabling further elaboration into distinct pharmaceutically active agents.

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Section: Resultsmentioning

confidence: 99%

Cobalt Homeostatic Catalysis for Coupling of Enaminones and Oxadiazolones to Quinazolinones

Fan

et al. 2022

Preprint

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“…More examples of directed C(sp 2 )–H amidation have been reported, including directed C–H amidation on substituted cyclopentadienyl ligands of ferrocene derivatives and C–H amidation reactions directly followed by cyclization steps to form heterocyclic compounds . Considering the mechanistic similarity of the C–H amidation mechanisms, we will not discuss these examples in detail herein.…”

Section: Directed C(sp2)–h Amidationmentioning

confidence: 99%

Dioxazolones: Stable Substrates for the Catalytic Transfer of Acyl Nitrenes

2020

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Dioxazolones are a convenient class of acyl nitrene transfer reagents. Their application in homogeneous transition-metal catalysis has led to many new amidation reactions. Dioxazolones are typically activated by transition metals at relatively low reaction temperatures. The metal nitrenoids formed by decarboxylative activation of dioxazolones are generally electron deficient and commonly react in a concerted fashion. “Intermolecular” nitrene insertion reactions involving preactivated C–H bonds (“inner-sphere” mechanism) easily compete with the Curtius-type rearrangement, but for intramolecular “direct” nitrene transfer/insertion reactions involving nonpreactivated substrates (i.e., without preceding formation of metal–carbon or metal–hydride bonds) extensive ligand optimization is important to prevent such unwanted side reactions. The ease of dioxazolone synthesis, formation of CO2 gas as the sole byproduct from reactions with dioxazolones, and the importance of nitrene transfer reactions in general has led to the development of several interesting reactions producing N-aryl amides, oxazoles, and lactams. Since the activation of dioxazolones proceeds under mild reaction conditions, stereo- and enantioselective reactions are also possible, which is useful for the synthesis of bioactive nitrogen-containing compounds. This review provides an overview of these reactions reported in recent years.

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“…In a separate study, Whiteoak group [16b] utilized the identical cobalt catalyst for the one‐pot synthesis of 1,2,3‐benzotriazin‐4(3H)‐ones 28 via a C−H amidation reaction as the key step, along with a reaction with TBN ( tert ‐butyl nitrite) (Scheme 11b). Furthermore, Liu research group [16c] synthesized quinazolinone 29 by employing a similar strategy using benzamides 27 and Co(III)‐catalyst in DCE via amidation followed by annulation protocol in one pot (Scheme 11c). Additionally, this method was exercised for the formation of quinazolinone‐based drug molecules and late‐stage modification of natural products.…”

Section: Cp*co(iii)‐catalyzed Directed Ortho Sp2(c)–h Amidation/amina...mentioning

confidence: 99%

Recent Progress in the C−N Bond Formation via High‐Valent Group 9 Cp*M(III)‐Catalyzed Directed sp² C−H Activation

Bera

Suchand

et al. 2020

Asian J Org Chem

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The presence of nitrogen atom in a wide variety of organic compounds called for the use of powerful CÀ H activation strategy in the CÀ N bond formation. Pentamethylcyclopentadienyl (Cp*) based, high-valent, group 9 transition-metal complexes have shown a great potential as catalysts in the CÀ H activation/functionalization over the years. This minireview summarizes recent progress made in the context of CÀ N bond formation via catalytic (sp 2)CÀ H activation with Cp*M(III) (M = Co, Rh and Ir) catalysts. A general plausible mechanism is briefly discussed at the beginning, and then results are arranged according to metal cobalt, rhodium and iridium, respectively.

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Cp*Co^III-catalyzed formal [4+2] cycloaddition of benzamides to afford quinazolinone derivatives

Abstract: A Cp*CoIII-catalyzed arene C–H bond amidation/annulation of benzamides was developed to afford quinazolinone derivatives in one-pot with high yields and broad substrate scope.

Cited by 33 publications

References 83 publications

Cobalt Homeostatic Catalysis for Coupling of Enaminones and Oxadiazolones to Quinazolinones

Cobalt Homeostatic Catalysis for Coupling of Enaminones and Oxadiazolones to Quinazolinones

Dioxazolones: Stable Substrates for the Catalytic Transfer of Acyl Nitrenes

Recent Progress in the C−N Bond Formation via High‐Valent Group 9 Cp*M(III)‐Catalyzed Directed sp² C−H Activation

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Cp*CoIII-catalyzed formal [4+2] cycloaddition of benzamides to afford quinazolinone derivatives

Abstract: A Cp*CoIII-catalyzed arene C–H bond amidation/annulation of benzamides was developed to afford quinazolinone derivatives in one-pot with high yields and broad substrate scope.

Cited by 33 publications

References 83 publications

Cobalt Homeostatic Catalysis for Coupling of Enaminones and Oxadiazolones to Quinazolinones

Cobalt Homeostatic Catalysis for Coupling of Enaminones and Oxadiazolones to Quinazolinones

Dioxazolones: Stable Substrates for the Catalytic Transfer of Acyl Nitrenes

Recent Progress in the C−N Bond Formation via High‐Valent Group 9 Cp*M(III)‐Catalyzed Directed sp2 C−H Activation

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Product

Resources

About

Cp*Co^III-catalyzed formal [4+2] cycloaddition of benzamides to afford quinazolinone derivatives

Recent Progress in the C−N Bond Formation via High‐Valent Group 9 Cp*M(III)‐Catalyzed Directed sp² C−H Activation