7-Azaindole. II. Conversion to 7-Methyl-7H-pyrrolo [2,3-b]pyridine and Related Compounds<sup>1,2</sup>

Robison, Michael M.; Robison, Bonnie L.

doi:10.1021/ja01629a040

Cited by 45 publications

(11 citation statements)

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“…Both N,-methyl-7-aziiindolc (NM7Al. 3) and 7-methyl-7H-pyrrolo C2.3-67) pyridine (N,-methyl-tautomer), (NMT,4) were prepared according to the method of Robison and Robison (1955); NM7AI was purified by vacuum distillation and NMT by PC.…”

Section: Methodsmentioning

confidence: 99%

Excited State Interactions of 7‐azaindole With Alcohol and Water

Avouris

Yang

El‐Bayoumi

1976

Photochem & Photobiology

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Abstract— The fluorescence spectrum of 7‐azaindole in alcohol is composed of two fluorescence bands. Effects of pH, temperature and solvent deuteration on the fluorescence spectra and quantum yields of 7‐azaindole and other model compounds in ethanol and in water are reported. The long wavelength band arises from a tautomeric species formed in an adiabatic photoreaction involving double proton transfer between one molecule of 7‐azaindole and one molecule of alcohol. The fluorescence spectrum of 7‐azaindole in water is composed of only one band, but the emission is weak and shows a large solvent isotope effect. The possibility of a double proton transfer reaction between 7‐azaindole and water is discussed.

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Section: Methodsmentioning

confidence: 99%

Excited State Interactions of 7‐azaindole With Alcohol and Water

Avouris

Yang

El‐Bayoumi

1976

Photochem & Photobiology

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“…To test the DMG dance concept, the regioisomeric N7 ( 2 a , b ) and N1 ( 6 a,b ) carbamoyl azaindoles were prepared (Figure C; for optimization see the Supporting Information) . The choice of CONR 2 as the DMG was dictated by its previous efficacy in D o M chemistry .…”

Section: Figurementioning

confidence: 99%

Regioselective Functionalization of 7‐Azaindole by Controlled Annular Isomerism: The Directed Metalation‐Group Dance

et al. 2019

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The regioselective functionalization of 7‐azaindole by controlled annular isomerism employing a directed metalation‐group migration is reported. The N7 carbamoyl azaindoles undergo regioselective metalation and quenching with an electrophile to furnish C6‐substituted derivatives which, in the presence of a catalytic amount of ClCONR2 promotes a carbamoyl group shift or dance from N7 to N1. A second directed metalation/electrophile quench sequence leads to 2,6‐substituted azaindoles. Optimization of the metalation conditions for C2 and C6, separately and iteratively, is presented. Using the directed metalation group dance strategy, a late‐stage deuteration of an antipsychotic drug is described. Overall, the controlled migration of the carbamoyl directing group allows multiple functionalization events of the bioactive azaindole scaffold.

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“…To test the DMG dance concept, the regioisomeric N7 (2a,b)a nd N1 (6a,b)c arbamoyl azaindoles were prepared ( Figure 1C;f or optimization see the Supporting Information). [11] Thechoice of CONR 2 as the DMG was dictated by its previous efficacyinDoMchemistry. [4b, 12] Although N1-DMGbearing 7-azaindoles have been synthesized previously, [4b, 13] to the best of our knowledge,N 7-DMG-bearing 7-azaindole isomers are unknown.…”

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confidence: 99%

Regioselective Functionalization of 7‐Azaindole by Controlled Annular Isomerism: The Directed Metalation‐Group Dance

et al. 2019

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The regioselective functionalization of 7-azaindole by controlled annular isomerism employing ad irected metalation-group migration is reported. The N7 carbamoyl azaindoles undergo regioselective metalation and quenchingwith an electrophile to furnish C6-substituted derivatives which, in the presence of ac atalytic amount of ClCONR 2 promotes ac arbamoyl group shift or dance from N7 to N1. As econd directed metalation/electrophile quench sequence leads to 2,6substituted azaindoles.O ptimization of the metalation conditions for C2 and C6, separately and iteratively,i sp resented. Using the directed metalation group dance strategy,alate-stage deuteration of an antipsychotic drug is described. Overall, the controlled migration of the carbamoyl directing group allows multiple functionalization events of the bioactive azaindole scaffold.Azaindoles occupy ap rominent position in drug discovery research because of their diverse bioactivities,e specially in protein kinase inhibition for the development of anticancer therapies.Among the four isosteres,the 7-azaindole scaffold, also present in arare class of natural products, [1] has emerged as the key heterocycle for structural modification towards new bioactive molecules ( Figure 1A). [2] Among the synthetic routes for 7-azaindoles,metalation-based methodologies have achieved dominance over classical processes because of the advantages of regioselectivity,m ultiple substitution, and ready modification of the prototype nucleus. [3,4] In previous efforts,w ed emonstrated the power of the directed ortho metalation (DoM) reaction in new halogen-dance strategies, [5] anionic ortho-Fries rearrangement processes, [6] latent directed metalation group (DMG) protocols, [7] and, as demonstrated on the 7-azaindole framework, walk-around-the-ringsequences. [4a,b,8] Whilst synthetically powerful, these metalationbased approaches involve several steps:D MG introduction, its use to direct the functionalization event, and its subsequent removal or modification.

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7-Azaindole. II. Conversion to 7-Methyl-7H-pyrrolo [2,3-b]pyridine and Related Compounds^1,2

Cited by 45 publications

References 0 publications

Excited State Interactions of 7‐azaindole With Alcohol and Water

Excited State Interactions of 7‐azaindole With Alcohol and Water

Regioselective Functionalization of 7‐Azaindole by Controlled Annular Isomerism: The Directed Metalation‐Group Dance

Regioselective Functionalization of 7‐Azaindole by Controlled Annular Isomerism: The Directed Metalation‐Group Dance

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7-Azaindole. II. Conversion to 7-Methyl-7H-pyrrolo [2,3-b]pyridine and Related Compounds1,2

Cited by 45 publications

References 0 publications

Excited State Interactions of 7‐azaindole With Alcohol and Water

Excited State Interactions of 7‐azaindole With Alcohol and Water

Regioselective Functionalization of 7‐Azaindole by Controlled Annular Isomerism: The Directed Metalation‐Group Dance

Regioselective Functionalization of 7‐Azaindole by Controlled Annular Isomerism: The Directed Metalation‐Group Dance

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7-Azaindole. II. Conversion to 7-Methyl-7H-pyrrolo [2,3-b]pyridine and Related Compounds^1,2