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Volumn 13, Issue 35, 2007, Pages 9973-9981

One-pot three-component catalytic synthesis of fully substituted pyrroles from readily available propargylic alcohols, 1,3-dicarbonyl compounds and primary amines

Author keywords

Alkynes; Annulation; Multicomponent reactions; Nitrogen heterocycles; Ruthenium

Indexed keywords

ALCOHOLS; AMINES; REACTION KINETICS; RUTHENIUM COMPOUNDS; SYNTHESIS (CHEMICAL);

EID: 37249029243     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200701132     Document Type: Article
Times cited : (90)

References (51)
  • 1
    • 4544235255 scopus 로고    scopus 로고
    • See, for example: a
    • See, for example: a) A. Fürstner, Angew. Chem. 2003, 115, 3706-3728;
    • (2003) Angew. Chem , vol.115 , pp. 3706-3728
    • Fürstner, A.1
  • 2
    • 17744417463 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2003, 42, 3582-3603;
    • (2003) Chem. Int. Ed , vol.42 , pp. 3582-3603
    • Angew1
  • 16
    • 37249081046 scopus 로고    scopus 로고
    • See, for example: a Pyrroles, The Synthesis Reactivity and Physical Properties of Substituted Pyrroles, Part II (Ed.: R. A. Jones), Wiley, New York, 1992;
    • See, for example: a) Pyrroles, The Synthesis Reactivity and Physical Properties of Substituted Pyrroles, Part II (Ed.: R. A. Jones), Wiley, New York, 1992;
  • 17
    • 0003288118 scopus 로고    scopus 로고
    • Eds, A. R. Katritzky, C. W. Rees, E. F. V. Scriven, Elsevier, Oxford
    • b) D. St. C. Black, Comprehensive Heterocyclic Chemistry II, Vol. 2 (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Elsevier, Oxford, 1996, pp. 39-117;
    • (1996) Comprehensive Heterocyclic Chemistry II , vol.2 , pp. 39-117
    • Black, D.S.C.1
  • 18
    • 0001426611 scopus 로고    scopus 로고
    • Eds, A. R. Katritzky, C.W. Rees, E. F. V. Scriven, Elsevier, Oxford
    • c) R. J. Sundberg, Comprehensive Heterocyclic Chemistry II, Vol.2 (Eds.: A. R. Katritzky, C.W. Rees, E. F. V. Scriven), Elsevier, Oxford, 1996, pp. 119-206;
    • (1996) Comprehensive Heterocyclic Chemistry II , vol.2 , pp. 119-206
    • Sundberg, R.J.1
  • 26
    • 24944474895 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2005, 44, 5664-5667;
    • (2005) Chem. Int. Ed , vol.44 , pp. 5664-5667
    • Angew1
  • 28
    • 33750623389 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2006, 45, 7079-7082.
    • (2006) Chem. Int. Ed , vol.45 , pp. 7079-7082
    • Angew1
  • 29
    • 22744450570 scopus 로고    scopus 로고
    • For recent reviews and highlights on pyrrole syntheses through MCRs, see: a
    • For recent reviews and highlights on pyrrole syntheses through MCRs, see: a) G. Balme, Angew. Chem. 2004, 116, 6396-6399;
    • (2004) Angew. Chem , vol.116 , pp. 6396-6399
    • Balme, G.1
  • 30
    • 11144250168 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2004, 43, 6238-6241;
    • (2004) Chem. Int. Ed , vol.43 , pp. 6238-6241
    • Angew1
  • 34
    • 33645069129 scopus 로고    scopus 로고
    • Brønsted acid catalysed propargylations of several organic substrates, including 1,3-dicarbonyl compounds, with alkynols have been reported: a R. Sanz, A. Martínez, J. M. Álvarez-Gutiérrez, F. Rodríguez, Eur. J. Org. Chem. 2006, 1383-1386;
    • Brønsted acid catalysed propargylations of several organic substrates, including 1,3-dicarbonyl compounds, with alkynols have been reported: a) R. Sanz, A. Martínez, J. M. Álvarez-Gutiérrez, F. Rodríguez, Eur. J. Org. Chem. 2006, 1383-1386;
  • 35
    • 33847795994 scopus 로고    scopus 로고
    • R. Sanz, D. Miguel, A. Martínez, J. M. Álvarez- Gutiérrez, F. Rodríguez, Org. Lett. 2007, 9, 727-730. In these works, only 5mol% of the acid is required to promote the propargylation process efficiently. In our case, the use of larger quantities of acid (50 mol%) is imperative in order to avoid the Meyer-Schuster isomerisation of the propargylic alcohol catalysed by ruthenium complex 1;
    • b) R. Sanz, D. Miguel, A. Martínez, J. M. Álvarez- Gutiérrez, F. Rodríguez, Org. Lett. 2007, 9, 727-730. In these works, only 5mol% of the acid is required to promote the propargylation process efficiently. In our case, the use of larger quantities of acid (50 mol%) is imperative in order to avoid the Meyer-Schuster isomerisation of the propargylic alcohol catalysed by ruthenium complex 1;
  • 38
    • 37249091068 scopus 로고    scopus 로고
    • This unusual transformation has been previously observed by us while studying the coupling process depicted in Scheme 1 see reference [7, The intermediate carboxylic acid 5 could not be detected by GC/MS, which indicates that its decarboxylation is a highly favoured process
    • This unusual transformation has been previously observed by us while studying the coupling process depicted in Scheme 1 (see reference [7]). The intermediate carboxylic acid 5 could not be detected by GC/MS, which indicates that its decarboxylation is a highly favoured process.
  • 39
    • 37249084977 scopus 로고    scopus 로고
    • The enantiomeric excess of 7q (> 99% ee; determined by chiral HPLC analysis) was identical to that of the starting amine, a result that confirms the complete stereospecificity of the reaction sequence.
    • The enantiomeric excess of 7q (> 99% ee; determined by chiral HPLC analysis) was identical to that of the starting amine, a result that confirms the complete stereospecificity of the reaction sequence.
  • 40
    • 24944579952 scopus 로고    scopus 로고
    • Metal-mediated cleavage of propargylic C-N bonds is a well-documented process. For a review on this topic, see
    • Metal-mediated cleavage of propargylic C-N bonds is a well-documented process. For a review on this topic, see: S. Escoubet, S. Gastaldi, M. Bertrand, Eur. J. Org. Chem. 2005, 3855-3873.
    • (2005) Eur. J. Org. Chem , pp. 3855-3873
    • Escoubet, S.1    Gastaldi, S.2    Bertrand, M.3
  • 41
    • 0000078290 scopus 로고    scopus 로고
    • 2 with primary amines to produce 1,2,3,5-substituted pyrroles: a) A. Arcadi, S. D. Giuseppe, F. Marinelli, E. Rossi, Adv. Synth. Catal. 2001, 343, 443-446;
    • 2 with primary amines to produce 1,2,3,5-substituted pyrroles: a) A. Arcadi, S. D. Giuseppe, F. Marinelli, E. Rossi, Adv. Synth. Catal. 2001, 343, 443-446;
  • 42
    • 0035976093 scopus 로고    scopus 로고
    • A. Arcadi, S. Di Giuseppe, F. Marinelli, E. Rossi, Tetrahedron: Asymmetry 2001, 12, 2715-2720. The intermediate β-enamino ester 11 was not detected by GC/MS, which indicates its great tendency to undergo the annulation.
    • b) A. Arcadi, S. Di Giuseppe, F. Marinelli, E. Rossi, Tetrahedron: Asymmetry 2001, 12, 2715-2720. The intermediate β-enamino ester 11 was not detected by GC/MS, which indicates its great tendency to undergo the annulation.
  • 43
    • 26444601347 scopus 로고    scopus 로고
    • We have observed that transformation of 10 into 3d is a highly favoured process that can be exclusively promoted by CF 3CO2H (50 mol, in THF at 75°C, Nevertheless, under these conditions, the sequential amination/annulation reaction takes place very slowly and yields 3d in only 43% yield (as determined by GC) after 24 h compare with entry 4 in Table 1, This fact clearly indicates an active role of the Lewis acid-ruthenium species in the reaction sequence. We note that related sequential amination/annulation reactions of 2-propynyl-1,3-dicarbonyl compounds with amines catalysed by trifluoroacetic acid have been described: A. S. Demir, A. Aybey, M. Kayalar, ARKlVOC 2005, 15, 105-116. It is also interesting to note that treatment of 10 with aniline, in THF at 75°C, in the absence of both CF3CO2H and complex 1 leads directly to pyrrole 3d without detection of the intermed
    • 2H and complex 1 leads directly to pyrrole 3d without detection of the intermediate β-enamino ester 11, albeit in very low yield (approximately 20%; as determined by GC) after 24 h (compare with the catalysed reaction in entry 4 in Table 1; 2 h, 94% yield of isolated product).
  • 45
    • 0035909591 scopus 로고    scopus 로고
    • A one-pot four-component synthesis of 1,2,3,5-tetrasubstituted pyrroles from secondary propargylic alcohols, aryl halides, aldehydes and primary amines has been reported. The process, which is catalysed by a Pd/Cu/thiazolium salt/acetic acid system, generates the corresponding tetrasubstituted pyrroles only in moderate yields (49-59%): R. U. Braun, K. Zeitler, T.J.J. Müller, Org. Lett. 2001, 3, 3297-3300.
    • A one-pot four-component synthesis of 1,2,3,5-tetrasubstituted pyrroles from secondary propargylic alcohols, aryl halides, aldehydes and primary amines has been reported. The process, which is catalysed by a Pd/Cu/thiazolium salt/acetic acid system, generates the corresponding tetrasubstituted pyrroles only in moderate yields (49-59%): R. U. Braun, K. Zeitler, T.J.J. Müller, Org. Lett. 2001, 3, 3297-3300.
  • 46
    • 37249013735 scopus 로고    scopus 로고
    • A closely related one-pot three-component synthesis of fully substituted pyrroles from alkynol 2a, aniline and enolisable ketones, employing [Cp*RuCl(μ2-SMe)2RuCp*Cl, Cp: pentamethylcyclopentadienyl; 10 mol, NH4BF4 (20mol, and PtCl2 (20 mol, has been described. We note that 1) no 1,3-dicarbonyl compounds were used as substrates in this catalytic reaction, 2) large excesses of both the ketone (used as solvent) and aniline (5 equiv relative to 2 a) are required and 3) only moderate yields 44-58, are attained after 100 h under refluxing conditions: Y. Nishibayashi, M. Yoshikawa, Y. Inada, M. D. Milton, M. Hidai, S. Uemura. Angew. Chem. 2003, 115, 2785-2788;
    • 2 (20 mol%), has been described. We note that 1) no 1,3-dicarbonyl compounds were used as substrates in this catalytic reaction, 2) large excesses of both the ketone (used as solvent) and aniline (5 equiv relative to 2 a) are required and 3) only moderate yields (44-58%) are attained after 100 h under refluxing conditions: Y. Nishibayashi, M. Yoshikawa, Y. Inada, M. D. Milton, M. Hidai, S. Uemura. Angew. Chem. 2003, 115, 2785-2788;
  • 47
    • 0038112039 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2003, 42, 2681-2684.
    • (2003) Chem. Int. Ed , vol.42 , pp. 2681-2684
    • Angew1


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