메뉴 건너뛰기




Volumn 72, Issue 10, 2007, Pages 3702-3712

Studies on the intramolecular cyclizations of bicyclic δ- hydroxynitriles promoted by triflic anhydride

Author keywords

[No Author keywords available]

Indexed keywords

CATALYST ACTIVITY; CHEMICAL ACTIVATION; CONFORMATIONS; CYCLIZATION; DICHLOROMETHANE; REACTION KINETICS;

EID: 84961986781     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo062669f     Document Type: Article
Times cited : (12)

References (64)
  • 3
    • 84962445579 scopus 로고    scopus 로고
    • For reviews of the Ritter reactions, see: (a) Krimen, L. 1.; Cota, D. J. In Organic Reactions; Dauben, W. G., Ed.; John Wiley & Sons: New York, 1969; 17, pp 213-325.
    • For reviews of the Ritter reactions, see: (a) Krimen, L. 1.; Cota, D. J. In Organic Reactions; Dauben, W. G., Ed.; John Wiley & Sons: New York, 1969; Vol. 17, pp 213-325.
  • 4
    • 0000818237 scopus 로고
    • Trost, B. M, Fleming, I, Eds, Pergamon Press: New York
    • (b) Bishop, R. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 6, pp 261-300.
    • (1991) Comprehensive Organic Synthesis , vol.6 , pp. 261-300
    • Bishop, R.1
  • 5
    • 0001916292 scopus 로고
    • For alternative methodologies developed for the Ritter reaction, see: a
    • For alternative methodologies developed for the Ritter reaction, see: (a) Top, S.; Jaouen, G. J. Org. Chem. 1981, 46, 78-82.
    • (1981) J. Org. Chem , vol.46 , pp. 78-82
    • Top, S.1    Jaouen, G.2
  • 15
    • 84962368533 scopus 로고    scopus 로고
    • unpublished results
    • Justribó, V., unpublished results.
    • Justribó, V.1
  • 19
    • 0032753886 scopus 로고    scopus 로고
    • Murakata, M.; Mizuno, Y.; Yamaguchi, H.; Hoshino, O. Chem. Pharm. Bull. 1999, 47, 1380-1383. In this publication, the (S)-enantiomer of enone 3 was described. This reference was unintentionally omitted in our previous publication (ref 8).
    • Murakata, M.; Mizuno, Y.; Yamaguchi, H.; Hoshino, O. Chem. Pharm. Bull. 1999, 47, 1380-1383. In this publication, the (S)-enantiomer of enone 3 was described. This reference was unintentionally omitted in our previous publication (ref 8).
  • 23
    • 84962460078 scopus 로고    scopus 로고
    • To simplify the analysis presented in this paper, we have not included the results of the reactions of other δ-hydroxynitriles that have been synthesized in our laboratory ref 5, These include a variety of acyclic and monocyclic substrates with secondary and tertiary alcohol functionalities. None of these δ-hydroxynitriles gave rise to enones upon treatment with triflic anhydride. The results of these experiments will be published elsewhere in due course
    • To simplify the analysis presented in this paper, we have not included the results of the reactions of other δ-hydroxynitriles that have been synthesized in our laboratory (ref 5). These include a variety of acyclic and monocyclic substrates with secondary and tertiary alcohol functionalities. None of these δ-hydroxynitriles gave rise to enones upon treatment with triflic anhydride. The results of these experiments will be published elsewhere in due course.
  • 24
    • 1542609701 scopus 로고    scopus 로고
    • The reaction mixtures needed to be acidified with aqueous HCl solution during the workup because otherwise the isolation of products as described in ref 4a was difficult and the yields were low. For a reference, see: Anderson, A. G, Greef, H. F. J. Am. Chem. Soc. 1952, 74, 5203-5204
    • The reaction mixtures needed to be acidified with aqueous HCl solution during the workup because otherwise the isolation of products as described in ref 4a was difficult and the yields were low. For a reference, see: Anderson, A. G.; Greef, H. F. J. Am. Chem. Soc. 1952, 74, 5203-5204.
  • 25
    • 33645545261 scopus 로고    scopus 로고
    • This protocol was developed after much experimentation while working on the Michael addition of methyl 2-oxocyclopentanecarboxylate to acrylonitrile because use of typical bases led to the opening of the ring. For a reference, see: Adamcik, J. A, Miklasiewicz, E. J. J. Org. Chem. 1963, 28, 336-339
    • This protocol was developed after much experimentation while working on the Michael addition of methyl 2-oxocyclopentanecarboxylate to acrylonitrile because use of typical bases led to the opening of the ring. For a reference, see: Adamcik, J. A.; Miklasiewicz, E. J. J. Org. Chem. 1963, 28, 336-339.
  • 28
    • 0037031621 scopus 로고    scopus 로고
    • and references cited therein
    • Overman, L. E.; Wolfe, J. P. J. Org. Chem. 2002, 67, 6421-6429 and references cited therein.
    • (2002) J. Org. Chem , vol.67 , pp. 6421-6429
    • Overman, L.E.1    Wolfe, J.P.2
  • 29
    • 84962366315 scopus 로고    scopus 로고
    • Carbocations 28-30 could also be formed directly from intermediates 22-24.
    • Carbocations 28-30 could also be formed directly from intermediates 22-24.
  • 30
    • 0001174653 scopus 로고
    • and references cited therein
    • Roger, R.; Neilson, D. G. Chem. Rev. 1961, 61, 179-211 and references cited therein.
    • (1961) Chem. Rev , vol.61 , pp. 179-211
    • Roger, R.1    Neilson, D.G.2
  • 35
    • 33646525410 scopus 로고    scopus 로고
    • and references cited therein
    • (b) Gutta, P.; Tantillo, D. J. J. Am. Chem. Soc. 2006, 128, 6172-6179 and references cited therein.
    • (2006) J. Am. Chem. Soc , vol.128 , pp. 6172-6179
    • Gutta, P.1    Tantillo, D.J.2
  • 40
    • 84962445598 scopus 로고    scopus 로고
    • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb. M. A, Cheeseman, J. R, Montgomery, J. A, Jr, Vreven, T, Kudin, K, N, Burant, J. C, Millam, J. M, Iyengar, S. S, Tomasi, J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, G. A, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li X, Knox, J. E, Hratchian, H. P, Cross, J. B, Adamo, C, Jaramillo, J, Gomperts, R, Stratmann, R. E, Yazyev, O, Austin, A. J, Cammi, R, Pomelli, C, Ochterski, J. W, Ayala, P. Y, Morokuma, K, Voth, G. A, Salvador, P, Dannenberg, J. J, Zakrzewski, V. G, Dapprich, S, Daniels. A. D, Strain, M. C, Farkas, O, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Ortiz, J. V, Cui, Q, Baboul, A. G, Clifford, S, Cioslowski, J, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Martin, R. L, Fox, D. J, Keith, T, Al-La
    • Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb. M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K.; N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels. A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision 6.1; Gaussian, Inc.: Pittsburgh, PA, 2003.
  • 41
    • 84962366309 scopus 로고    scopus 로고
    • Hyperchem Professional Release 7.52; Hypercube, Inc, 2005
    • Hyperchem Professional Release 7.52; Hypercube, Inc., 2005.
  • 43
    • 84962445588 scopus 로고    scopus 로고
    • Location of protonated triflates 22, 23, and 24 was somewhat complicated because many conformers dissociated to the corresponding carbocations plus triflic acid during minimizations.
    • Location of protonated triflates 22, 23, and 24 was somewhat complicated because many conformers dissociated to the corresponding carbocations plus triflic acid during minimizations.
  • 48
    • 84962338596 scopus 로고    scopus 로고
    • All located transition structures had only one imaginary frequency corresponding to the formation of the expected bonds
    • All located transition structures had only one imaginary frequency corresponding to the formation of the expected bonds.
  • 49
    • 33845979150 scopus 로고    scopus 로고
    • The negative sign of the computed activation energies might be a consequence of the flatness of the PES and also of the method employed in the calculations because B3LYP is known to underestimate energy barriers. For some recent references, see: (a) Pemberton, R. P, McShane, C. M, Castro, C, Karney, W. L. J. Am. Chem. Soc. 2006, 128, 16692-16700
    • The negative sign of the computed activation energies might be a consequence of the flatness of the PES and also of the method employed in the calculations because B3LYP is known to underestimate energy barriers. For some recent references, see: (a) Pemberton, R. P.; McShane, C. M.; Castro, C.; Karney, W. L. J. Am. Chem. Soc. 2006, 128, 16692-16700.
  • 54
    • 84962403109 scopus 로고    scopus 로고
    • -1, suggesting that these processes should be energetically feasible at room temperature.
    • -1, suggesting that these processes should be energetically feasible at room temperature.
  • 55
    • 0037120838 scopus 로고    scopus 로고
    • Activation of the cyano group by protonation has been shown to be the rate-limiting step in some reactions involving nucleophilic attack on nitriles. For example, see: Himo, F, Demko, Z. P, Noodleman, L, Sharpless, K. B. J. Am. Chem. Soc. 2002, 124, 12210-12216 and references cited therein
    • Activation of the cyano group by protonation has been shown to be the rate-limiting step in some reactions involving nucleophilic attack on nitriles. For example, see: Himo, F.; Demko, Z. P.; Noodleman, L.; Sharpless, K. B. J. Am. Chem. Soc. 2002, 124, 12210-12216 and references cited therein.
  • 56
    • 84962404748 scopus 로고    scopus 로고
    • The localization of the transition structures leading to the protonation of the alcohols and the formation of the protonated triflates would lead to a clearer picture of the competence observed between these processes. However, based on Hammond's Postulate, transition structures should be closer in energy to the products than to the reactants because we computed both activation steps to be endergonic ΔG > 0, Reaction energies were thus used to estimate the reactivity trend for each process
    • The localization of the transition structures leading to the protonation of the alcohols and the formation of the protonated triflates would lead to a clearer picture of the competence observed between these processes. However, based on Hammond's Postulate, transition structures should be closer in energy to the products than to the reactants because we computed both activation steps to be endergonic (ΔG > 0). Reaction energies were thus used to estimate the reactivity trend for each process.
  • 57
    • 4043066337 scopus 로고    scopus 로고
    • Cleavage of protonated alcohols to the carbocations and water was observed during some geometry optimizations. The same results have been obtained in a number of studies. For example, see: Fujio, M, Keeffe, J. R, More O'Ferrall. R. A, O'Donoghue, A. C. J. Am. Chem. Soc. 2004, 126, 9982-9992
    • Cleavage of protonated alcohols to the carbocations and water was observed during some geometry optimizations. The same results have been obtained in a number of studies. For example, see: Fujio, M.; Keeffe, J. R.; More O'Ferrall. R. A.; O'Donoghue, A. C. J. Am. Chem. Soc. 2004, 126, 9982-9992.
  • 58
    • 84962403095 scopus 로고    scopus 로고
    • It is well known that imidates rearrange readily to amides. This rearrangement has been extensively studied and is known as the Chapman or Lander rearrangement depending on the nature of the carbon that shifts from the oxygen to the nitrogen. The mechanism of this reaction also appears to depend on the nature of the substituent
    • It is well known that imidates rearrange readily to amides. This rearrangement has been extensively studied and is known as the Chapman or Lander rearrangement depending on the nature of the carbon that shifts from the oxygen to the nitrogen. The mechanism of this reaction also appears to depend on the nature of the substituent.
  • 59
    • 33947301041 scopus 로고
    • L'abbe, G. Chem. Rev. 1969, 69, 345-363.
    • (1969) Chem. Rev , vol.69 , pp. 345-363
    • L'abbe, G.1
  • 61
    • 0035826331 scopus 로고    scopus 로고
    • For a related attack of an ambident nucleophile see
    • For a related attack of an ambident nucleophile see: Peng, Z-H.; Woerpel, K. A. Org. Lett. 2001, 3, 675-678.
    • (2001) Org. Lett , vol.3 , pp. 675-678
    • Peng, Z.-H.1    Woerpel, K.A.2
  • 62
    • 0010851829 scopus 로고    scopus 로고
    • -1 more stable in the gas phase. This is in agreement with the literature. For example, see: (a) Beak, P.; Lee, J.; Zeigler, J. M. J. Org. Chem. 1980, 43, 1536-1538.
    • -1 more stable in the gas phase. This is in agreement with the literature. For example, see: (a) Beak, P.; Lee, J.; Zeigler, J. M. J. Org. Chem. 1980, 43, 1536-1538.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.