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Volumn , Issue 22, 2002, Pages 3731-3733

Unexpected hydrolysis of a C(7)-oxo-substituted 2-oxonorborn-1-yl triflate: Norbornane-ring expansion versus norbornane-ring contraction

Author keywords

Chiral pool; Hydrolysis; Ring expansion; Strained molecules; Substituent effects

Indexed keywords

CARBOXYLIC ACID; LACTONE DERIVATIVE; NORBORNANE DERIVATIVE; TRIFLUOROMETHANESULFONIC ACID;

EID: 0036856586     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0690(200211)2002:22<3731::AID-EJOC3731>3.0.CO;2-1     Document Type: Article
Times cited : (5)

References (27)
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    • Bridgehead-subsituted norbornanes: [3a] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, Tetrahedron: Asymmetry 1998, 9, 1737-1745 and references cited therein. Norbornane-derived chiral catalysts: [3b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, P. Chicharro Villas, Tetrahedron: Asymmetry 2002, 13, 1-4 and references cited therein. C(10)-substituted camphors and fenchones: [3c] A. García Martínez, E. Teso Vilar, A. Garcia Fraile, S. de la Moya Cerero, B. Lora Maroto, Tetrahedron: Asymmetry 2002, 13, 17-19 and references cited therein. Cyclopentanoids from 1-norbornyl triflates: [3d] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, S. de Oro Osuna, B. Lora Maroto, Tetrahedron Lett. 2001, 42, 7795-7799 and references cited therein. Bicyclo[2.1.1]hexanes from 1-norbornyl triflates: [3e] Garcia Martinez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, L. R. Subramanian, Synlett 1994, 563-464 and ref.[2b]
    • (1998) Tetrahedron: Asymmetry , vol.9 , pp. 1737-1745
    • García Martínez, A.1    Teso Vilar, E.2    García Fraile, A.3    De la Moya Cerero, S.4    Martínez Ruiz, P.5
  • 12
    • 0037070071 scopus 로고    scopus 로고
    • and references cited therein
    • Bridgehead-subsituted norbornanes: [3a] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martinez Ruiz, Tetrahedron: Asymmetry 1998, 9, 1737-1745 and references cited therein. Norbornane-derived chiral catalysts: [3b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, P. Chicharro Villas, Tetrahedron: Asymmetry 2002, 13, 1-4 and references cited therein. C(10)-substituted camphors and fenchones: [3c] A. García Martínez, E. Teso Vilar, A. Garcia Fraile, S. de la Moya Cerero, B. Lora Maroto, Tetrahedron: Asymmetry 2002, 13, 17-19 and references cited therein. Cyclopentanoids from 1-norbornyl triflates: [3d] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, S. de Oro Osuna, B. Lora Maroto, Tetrahedron Lett. 2001, 42, 7795-7799 and references cited therein. Bicyclo[2.1.1]hexanes from 1-norbornyl triflates: [3e] Garcia Martinez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, L. R. Subramanian, Synlett 1994, 563-464 and ref.[2b]
    • (2002) Tetrahedron: Asymmetry , vol.13 , pp. 1-4
    • García Martínez, A.1    Teso Vilar, E.2    García Fraile, A.3    De la Moya Cerero, S.4    Martínez Ruiz, P.5    Chicharro Villas, P.6
  • 13
    • 0037070077 scopus 로고    scopus 로고
    • and references cited therein
    • Bridgehead-subsituted norbornanes: [3a] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martinez Ruiz, Tetrahedron: Asymmetry 1998, 9, 1737-1745 and references cited therein. Norbornane-derived chiral catalysts: [3b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, P. Chicharro Villas, Tetrahedron: Asymmetry 2002, 13, 1-4 and references cited therein. C(10)-substituted camphors and fenchones: [3c] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, B. Lora Maroto, Tetrahedron: Asymmetry 2002, 13, 17-19 and references cited therein. Cyclopentanoids from 1-norbornyl triflates: [3d] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, S. de Oro Osuna, B. Lora Maroto, Tetrahedron Lett. 2001, 42, 7795-7799 and references cited therein. Bicyclo[2.1.1]hexanes from 1-norbornyl triflates: [3e] Garcia Martinez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, L. R. Subramanian, Synlett 1994, 563-464 and ref.[2b]
    • (2002) Tetrahedron: Asymmetry , vol.13 , pp. 17-19
    • García Martínez, A.1    Teso Vilar, E.2    García Fraile, A.3    De la Moya Cerero, S.4    Lora Maroto, B.5
  • 14
    • 0011892689 scopus 로고    scopus 로고
    • and references cited therein
    • Bridgehead-subsituted norbornanes: [3a] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martinez Ruiz, Tetrahedron: Asymmetry 1998, 9, 1737-1745 and references cited therein. Norbornane-derived chiral catalysts: [3b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, P. Chicharro Villas, Tetrahedron: Asymmetry 2002, 13, 1-4 and references cited therein. C(10)-substituted camphors and fenchones: [3c] A. García Martínez, E. Teso Vilar, A. Garcia Fraile, S. de la Moya Cerero, B. Lora Maroto, Tetrahedron: Asymmetry 2002, 13, 17-19 and references cited therein. Cyclopentanoids from 1-norbornyl triflates: [3d] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, S. de Oro Osuna, B. Lora Maroto, Tetrahedron Lett. 2001, 42, 7795-7799 and references cited therein. Bicyclo[2.1.1]hexanes from 1-norbornyl triflates: [3e] Garcia Martinez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, L. R. Subramanian, Synlett 1994, 563-464 and ref.[2b]
    • (2001) Tetrahedron Lett. , vol.42 , pp. 795-7799
    • García Martínez, A.1    Teso Vilar, E.2    García Fraile, A.3    De la Moya Cerero, S.4    De Oro Osuna, S.5    Lora Maroto, B.6
  • 15
    • 0001695817 scopus 로고
    • and ref.[2b]
    • Bridgehead-subsituted norbornanes: [3a] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martinez Ruiz, Tetrahedron: Asymmetry 1998, 9, 1737-1745 and references cited therein. Norbornane-derived chiral catalysts: [3b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, P. Chicharro Villas, Tetrahedron: Asymmetry 2002, 13, 1-4 and references cited therein. C(10)-substituted camphors and fenchones: [3c] A. García Martínez, E. Teso Vilar, A. Garcia Fraile, S. de la Moya Cerero, B. Lora Maroto, Tetrahedron: Asymmetry 2002, 13, 17-19 and references cited therein. Cyclopentanoids from 1-norbornyl triflates: [3d] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, S. de Oro Osuna, B. Lora Maroto, Tetrahedron Lett. 2001, 42, 7795-7799 and references cited therein. Bicyclo[2.1.1]hexanes from 1-norbornyl triflates: [3e] Garcia Martinez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, L. R. Subramanian, Synlett 1994, 563-464 and ref.[2b]
    • (1994) Synlett , pp. 563-464
    • García Martínez, A.1    Teso Vilar, E.2    García Fraile, A.3    De la Moya Cerero, S.4    Subramanian, L.R.5
  • 16
    • 0027990553 scopus 로고
    • For the preparation of chiral ligands (diols and amino alcohols) from 1-norbornyl triflates see for example: [4a] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, L. R. Subramanian, Tetrahedron: Asymmetry 1994, 5, 1373-1376. [4b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, L. R. Subramanian, Tetrahedron: Asymmetry 1996, 7, 1257-1260 and ref.[3b] For the importance of tridentate norbornane-based ligands as chiral catalysts, see for example: [4c] I. Philipova, V. Dimitrov, S. Simova, Tetrahedron: Asymmetry 1999, 10, 913-921 and 1381-1391. Restricted norbornane-based triols can be interesting intermediates for the synthesis of artificial lyposomes (see for example: [4d] A. D. Miller, Angew. Chem. Int. Ed. 1998, 37, 1768-1785), whereas restricted aminodiols can be used in the synthesis of artificial sphingosines (see for example: [4e] N. Khiar, K. Singh, M. Garcia, M. Martín-Lomas, Tetrahedron Lett. 1999, 40, 5779-5782). On the other hand, chiral tridentate triols are interesting ligands for the preparation of transition-metal complex chiral catalysts (see for example: [4f] H. Lütjens, G. Wahl, F. Möller, P. Knöchel, J. Sundermeyer, Organometallics 1997, 16, 5869-5878).
    • (1994) Tetrahedron: Asymmetry , vol.5 , pp. 1373-1376
    • García Martínez, A.1    Teso Vilar, E.2    García Fraile, A.3    De la Moya Cerero, S.4    Subramanian, L.R.5
  • 17
    • 0000170238 scopus 로고    scopus 로고
    • and ref.[3b]
    • For the preparation of chiral ligands (diols and amino alcohols) from 1-norbornyl triflates see for example: [4a] A. García Martínez, E. Teso Vilar, A. Garcia Fraile, S. de la Moya Cerero, L. R. Subramanian, Tetrahedron: Asymmetry 1994, 5, 1373-1376. [4b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, L. R. Subramanian, Tetrahedron: Asymmetry 1996, 7, 1257-1260 and ref.[3b] For the importance of tridentate norbornane-based ligands as chiral catalysts, see for example: [4c] I. Philipova, V. Dimitrov, S. Simova, Tetrahedron: Asymmetry 1999, 10, 913-921 and 1381-1391. Restricted norbornane-based triols can be interesting intermediates for the synthesis of artificial lyposomes (see for example: [4d] A. D. Miller, Angew. Chem. Int. Ed. 1998, 37, 1768-1785), whereas restricted aminodiols can be used in the synthesis of artificial sphingosines (see for example: [4e] N. Khiar, K. Singh, M. Garcia, M. Martín-Lomas, Tetrahedron Lett. 1999, 40, 5779-5782). On the other hand, chiral tridentate triols are interesting ligands for the preparation of transition-metal complex chiral catalysts (see for example: [4f] H. Lütjens, G. Wahl, F. Möller, P. Knöchel, J. Sundermeyer, Organometallics 1997, 16, 5869-5878).
    • (1996) Tetrahedron: Asymmetry , vol.7 , pp. 1257-1260
    • García Martínez, A.1    Teso Vilar, E.2    García Fraile, A.3    De la Moya Cerero, S.4    Martínez Ruiz, P.5    Subramanian, L.R.6
  • 18
    • 0033548383 scopus 로고    scopus 로고
    • For the preparation of chiral ligands (diols and amino alcohols) from 1-norbornyl triflates see for example: [4a] A. García Martínez, E. Teso Vilar, A. Garcia Fraile, S. de la Moya Cerero, L. R. Subramanian, Tetrahedron: Asymmetry 1994, 5, 1373-1376. [4b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, L. R. Subramanian, Tetrahedron: Asymmetry 1996, 7, 1257-1260 and ref.[3b] For the importance of tridentate norbornane-based ligands as chiral catalysts, see for example: [4c] I. Philipova, V. Dimitrov, S. Simova, Tetrahedron: Asymmetry 1999, 10, 913-921 and 1381-1391. Restricted norbornane-based triols can be interesting intermediates for the synthesis of artificial lyposomes (see for example: [4d] A. D. Miller, Angew. Chem. Int. Ed. 1998, 37, 1768-1785), whereas restricted aminodiols can be used in the synthesis of artificial sphingosines (see for example: [4e] N. Khiar, K. Singh, M. Garcia, M. Martín-Lomas, Tetrahedron Lett. 1999, 40, 5779-5782). On the other hand, chiral tridentate triols are interesting ligands for the preparation of transition-metal complex chiral catalysts (see for example: [4f] H. Lütjens, G. Wahl, F. Möller, P. Knöchel, J. Sundermeyer, Organometallics 1997, 16, 5869-5878).
    • (1999) Tetrahedron: Asymmetry , vol.10 , pp. 913-921
    • Philipova, I.1    Dimitrov, V.2    Simova, S.3
  • 19
    • 0032479769 scopus 로고    scopus 로고
    • For the preparation of chiral ligands (diols and amino alcohols) from 1-norbornyl triflates see for example: [4a] A. García Martínez, E. Teso Vilar, A. Garcia Fraile, S. de la Moya Cerero, L. R. Subramanian, Tetrahedron: Asymmetry 1994, 5, 1373-1376. [4b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, L. R. Subramanian, Tetrahedron: Asymmetry 1996, 7, 1257-1260 and ref.[3b] For the importance of tridentate norbornane-based ligands as chiral catalysts, see for example: [4c] I. Philipova, V. Dimitrov, S. Simova, Tetrahedron: Asymmetry 1999, 10, 913-921 and 1381-1391. Restricted norbornane-based triols can be interesting intermediates for the synthesis of artificial lyposomes (see for example: [4d] A. D. Miller, Angew. Chem. Int. Ed. 1998, 37, 1768-1785), whereas restricted aminodiols can be used in the synthesis of artificial sphingosines (see for example: [4e] N. Khiar, K. Singh, M. Garcia, M. Martín-Lomas, Tetrahedron Lett. 1999, 40, 5779-5782). On the other hand, chiral tridentate triols are interesting ligands for the preparation of transition-metal complex chiral catalysts (see for example: [4f] H. Lütjens, G. Wahl, F. Möller, P. Knöchel, J. Sundermeyer, Organometallics 1997, 16, 5869-5878).
    • (1998) Angew. Chem. Int. Ed. , vol.37 , pp. 1768-1785
    • Miller, A.D.1
  • 20
    • 0033618299 scopus 로고    scopus 로고
    • For the preparation of chiral ligands (diols and amino alcohols) from 1-norbornyl triflates see for example: [4a] A. García Martínez, E. Teso Vilar, A. Garcia Fraile, S. de la Moya Cerero, L. R. Subramanian, Tetrahedron: Asymmetry 1994, 5, 1373-1376. [4b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, L. R. Subramanian, Tetrahedron: Asymmetry 1996, 7, 1257-1260 and ref.[3b] For the importance of tridentate norbornane-based ligands as chiral catalysts, see for example: [4c] I. Philipova, V. Dimitrov, S. Simova, Tetrahedron: Asymmetry 1999, 10, 913-921 and 1381-1391. Restricted norbornane-based triols can be interesting intermediates for the synthesis of artificial lyposomes (see for example: [4d] A. D. Miller, Angew. Chem. Int. Ed. 1998, 37, 1768-1785), whereas restricted aminodiols can be used in the synthesis of artificial sphingosines (see for example: [4e] N. Khiar, K. Singh, M. García, M. Martín-Lomas, Tetrahedron Lett. 1999, 40, 5779-5782). On the other hand, chiral tridentate triols are interesting ligands for the preparation of transition-metal complex chiral catalysts (see for example: [4f] H. Lütjens, G. Wahl, F. Möller, P. Knöchel, J. Sundermeyer, Organometallics 1997, 16, 5869-5878).
    • (1999) Tetrahedron Lett. , vol.40 , pp. 5779-5782
    • Khiar, N.1    Singh, K.2    García, M.3    Martín-Lomas, M.4
  • 21
    • 0041687313 scopus 로고    scopus 로고
    • For the preparation of chiral ligands (diols and amino alcohols) from 1-norbornyl triflates see for example: [4a] A. García Martínez, E. Teso Vilar, A. Garcia Fraile, S. de la Moya Cerero, L. R. Subramanian, Tetrahedron: Asymmetry 1994, 5, 1373-1376. [4b] A. García Martínez, E. Teso Vilar, A. García Fraile, S. de la Moya Cerero, P. Martínez Ruiz, L. R. Subramanian, Tetrahedron: Asymmetry 1996, 7, 1257-1260 and ref.[3b] For the importance of tridentate norbornane-based ligands as chiral catalysts, see for example: [4c] I. Philipova, V. Dimitrov, S. Simova, Tetrahedron: Asymmetry 1999, 10, 913-921 and 1381-1391. Restricted norbornane-based triols can be interesting intermediates for the synthesis of artificial lyposomes (see for example: [4d] A. D. Miller, Angew. Chem. Int. Ed. 1998, 37, 1768-1785), whereas restricted aminodiols can be used in the synthesis of artificial sphingosines (see for example: [4e] N. Khiar, K. Singh, M. Garcia, M. Martín-Lomas, Tetrahedron Lett. 1999, 40, 5779-5782). On the other hand, chiral tridentate triols are interesting ligands for the preparation of transition-metal complex chiral catalysts (see for example: [4f] H. Lütjens, G. Wahl, F. Möller, P. Knöchel, J. Sundermeyer, Organometallics 1997, 16, 5869-5878).
    • (1997) Organometallics , vol.16 , pp. 5869-5878
    • Lütjens, H.1    Wahl, G.2    Möller, F.3    Knöchel, P.4    Sundermeyer, J.5
  • 22
    • 0029821881 scopus 로고    scopus 로고
    • and references cited therein
    • For the preparation of 4 from camphor, see: M. Gianini, A. von Zelewsky, Synthesis 1996, 702-706, and references cited therein.
    • (1996) Synthesis , pp. 702-706
    • Gianini, M.1    Von Zelewsky, A.2
  • 23
    • 0011879834 scopus 로고    scopus 로고
    • note
    • 13C NMR spectra agree with the proposed structure.
  • 24
    • 0011798966 scopus 로고    scopus 로고
    • note
    • 13C NMR spectra agree with the structure).
  • 25
    • 0011800271 scopus 로고    scopus 로고
    • note
    • 2 1:4). After chromatography, pure 7 was obtained (0.13 g, 97% yield from 6) (for characterization data see ref.[7]).
  • 26
    • 1542587019 scopus 로고
    • Solvent addition to the carbonyl group before the trifiate-group cleavage has been previously proposed, although to the best of our knowledge not totally demonstrated, for the solvolysis of some 2-oxo- and 2-thioxo-substituted bridgehead triflates. See for example: [9a] X. Creary, Chem. Rev. 1991, 91, 1625-1677. [9b] K. Takunaga, T. Ohtsu, Y. Ohga, K. Takeuchi, J. Org. Chem. 1998, 63, 2209-2217. See also ref.[2d] and the references cited therein.
    • (1991) Chem. Rev. , vol.91 , pp. 1625-1677
    • Creary, X.1
  • 27
    • 0011836726 scopus 로고    scopus 로고
    • See also ref.[2d] and the references cited therein
    • Solvent addition to the carbonyl group before the trifiate-group cleavage has been previously proposed, although to the best of our knowledge not totally demonstrated, for the solvolysis of some 2-oxo- and 2-thioxo-substituted bridgehead triflates. See for example: [9a] X. Creary, Chem. Rev. 1991, 91, 1625-1677. [9b] K. Takunaga, T. Ohtsu, Y. Ohga, K. Takeuchi, J. Org. Chem. 1998, 63, 2209-2217. See also ref.[2d] and the references cited therein.
    • (1998) J. Org. Chem. , vol.63 , pp. 2209-2217
    • Takunaga, K.1    Ohtsu, T.2    Ohga, Y.3    Takeuchi, K.4


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