Double cationic propargylation: From linear to polycyclic ethers

Organic Letters

Volumn 3, Issue 21, 2001, Pages 3289-3291

  Díaz, David ^a   Martín, Tomás ^a   Martín, Víctor S ^a  

^a UNIVERSIDAD DE LA LAGUNA   (Spain)

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ARTICLE;

EID: 0001651540     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0164987     Document Type: Article

References (19)

1. (a) Caffyn, A. J. M.; Nicholas, K. M. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Ed.; Pergamon: Oxford, 1995; Vol. 12, Chapter 7.1, pp 685-702.
2. (b) Nicholas, K. M. Acc. Chem. Res. 1987, 20, 207-214.
3. (c) Green, J. R. Curr. Org. Chem. 2001, 5, 809-826.
4. (a) Palazón, J. M.; Martín, V. S. Tetrahedron Lett. 1995, 36, 3549-3552.
5. (b) Mukai, C.; Yamaguchi, S.; Sugimoto, Y.-I.; Miyakoshi, N.; Kasamatsu, E.; Hanaoka, M. J. Org. Chem. 2000, 65, 6761-6765, and references therein.
6. (c) Kira, K.; Isobe, M. Tetrahedron Lett. 2001, 42, 2821-2824, and references therein.
7. Díaz, D. D.; Martín, V. S. Tetrahedron Lett. 2000, 41, 9993-9996.
8. 2: C, 77.40; H, 5.41. Found: C, 77.20; H, 5.51.
9. 6-complexes were satisfactorily demetalized in the standard manner (CAN, acetone, 0 °C) to obtain the free acetylenes. See: Seyferth, D.; Nestle, M. O.; Wehman. J. Am. Chem. Soc. 1975, 97, 7417-7426.
10. During the formation of 3 it was possible to detect by TLC the transitory formation of the monoether that evolves to the diether. In consequence, the species 2 is a sequentially achieved formalism.
11. Although 6 is a known compound, the methods for its synthesis reported in the literature provided very poor yields. See: Gleiter, R.; Rittinger, S. Tetrahedron Lett. 1988, 29, 4529-4532.
12. For the synthesis of sulfur macrocycles containing dialkyne units, see: Davies, J. E.; Hope-Weeks, L. J.; Mays, M. J.; Raithby, P. R. J. Chem. Soc., Chem. Commun. 2000, 1411-1412.
13. For additional methods to synthesize cyclic ethers, see: (a) Alvarez, E.; Candenas, M. L.; Pérez, R.; Ravelo, J. L.; Martín, J. D. Chem. Rev. 1995, 95, 1953-1980, and references therein.
14. (b) Hoberg, J. O. Tetrahedron 1998, 54, 12631-12670.
15. (c) Yet, L. Chem. Rev. 2000, 100, 2963-3007, and references therein.
16. (d) Heck, M.-P.; Baylon, C.; Nolan, S. P.; Mioskowski, C. Org. Lett. 2001, 3, 1989-1991, and references therein.
17. A plausible mechanism implies catalytic participation of the Lewis acid, generating the cyclic ether and tetrahydropyran-2-ol: equation presented
18. 2, then NaH, MeOH, 52% overall. equation presented
19. The stereochemistry of 12 was determined by NOE studies (see Supporting Information).