Synthesis of bridged medium-sized rings through the intramolecular Pauson-Khand reaction

Organic Letters

Volumn 3, Issue 16, 2001, Pages 2607-2610

  Lovely, Carl J ^a   Seshadri, Hemalatha ^a   Wayland, Brian R ^a   Cordes, A Wallace ^b  

^a UNIVERSITY OF TEXAS AT ARLINGTON   (United States)

^b UNIVERSITY OF ARKANSAS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001294824     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol016308s     Document Type: Article

References (24)

1. For a recent review of this area, see: Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56, 3263.
2. Krafft, M. E.; Fu, Z.; Bonaga, V. R. Tetrahedron Lett. 2001, 42, 1427.
3. Cazes has reported the low yield synthesis of a bicyclo[5.3.0]decene from an allenyne. See: Ahmar, M.; Locatelli, C.; Colombier, D.; Cazes, B. Tetrahedron Lett. 1997, 38, 5281.
4. For an attempt to prepare seven-membered rings through the intramolecular Pauson-Khand reaction, see: Mukai, C.; Sonobe, H.; Kim, J. S.; Hanoaka, M. J. Org. Chem. 2000, 65, 6654. See also Wender, P. A.; McDonald, F. E. Tetrahedron Lett. 1990, 31, 3691.
5. For an attempt to prepare seven-membered rings through the intramolecular Pauson-Khand reaction, see: Mukai, C.; Sonobe, H.; Kim, J. S.; Hanoaka, M. J. Org. Chem. 2000, 65, 6654. See also Wender, P. A.; McDonald, F. E. Tetrahedron Lett. 1990, 31, 3691.
6. (a) Petasis, N. A.; Patane, M. A. Tetrahedron 1992, 48, 5757.
7. (b) Roxburgh, C. J. Tetrahedron 1993, 49, 10749.
8. (a) Jung, M. E. Synlett 1999, 843.
9. (b) Jung, M. E. Synlett 1990, 186.
10. Seshadri, H. Ph.D. Dissertation, The University of Texas at Arlington, Arlington, TX, 2001.
11. Lovely, C. J.; Seshadri, H. Synth. Commun. 2001, 31, xxxx. See also: Blanco-Urgoiti, J.; Casarrubios, L.; Domínguez, G.; Pérez-Castells, J. Tetrahedron Lett. 2001, 42, 3315.
12. Lovely, C. J.; Seshadri, H. Synth. Commun. 2001, 31, xxxx. See also: Blanco-Urgoiti, J.; Casarrubios, L.; Domínguez, G.; Pérez-Castells, J. Tetrahedron Lett. 2001, 42, 3315.
13. For studies relating to systems derived from o-vinylphenol, see: Pérez-Serrano, L.; Blanco-Urgoiti, J.; Casarrubios, L.; Domínguez, G.; Pérez-Castells, J. J. Org. Chem. 2000, 65, 3513.
14. Arcadi, A.; Cacchi, S.; Del Rosario, M.; Fabrizi, G.; Marinelli, F. J. Org. Chem. 1996, 61, 9280.
15. Orlek, B. S.; Sammes, P. G.; Weller, D. J. Tetrahedron 1993, 49, 8179.
16. For a review of this approach see Sammes, P. G.; Weller, D. J. Synthesis 1995, 1205.
17. The o-ethynylphenols were prepared by iodination of the corresponding phenol and then Sonogashira cross-coupling of the iodide with TMS-acetylene. See Supporting Information for details.
18. The absence of a three-proton doublet quickly ruled out migration of the double bond to an internal position followed by cyclization to provide a methylcyclopentenone: see ref 4.
19. At this point we are operating under the assumption that the epoxidation of the strained double bond is NMO promoted. However, control experiments indicate that this does not take place by direct reaction of the enone with NMO. For a related observation, see: Muto, R.; Ogasawara, K. Tetrahedron Lett. 2001, 42, 4143 and references therein.
20. Krafft has observed bridged products as a result of CO insertion at the internal position of both the alkyne and the alkene; see ref 2. See also: Forsyth, G. S.; Kerr, W. J.; Ladduwahetty, T. In Organometallics in Organic Synthesis; Bateson, J. H., Mitchell, M. B., Eds.; Academic Press: London, 1994; p 239. We are grateful to Prof. Marie Krafft for bringing this reference to our attention.
21. Particularly supportive of this assignment is the downfield signal for the β-enone proton (δ = 8.25 vs 6.30-6.47); see ref 8.
22. Presumably, with the allyl-containing substrates it is geometrically difficult to adopt a conformation related to 21 to produce a bridged adduct.
23. Krafft, M. E.; Romero, R. H.; Scott, I. L. J. Org. Chem. 1992, 57, 5277.
24. Robert, F.; Milet, A.; Gimbert, Y.; Konya, D.; Greene, A. E. J. Am. Chem. Soc. 2001, 123, 5396.