In situ cuprate formation via transmetalation between vinylstannanes and higher order cyanocuprates

Journal of the American Chemical Society

Volumn 110, Issue 8, 1988, Pages 2641-2643

  Behling, James R ^a   Babiak, Kevin A ^a   Ng, John S ^a   Campbell, Arthur L ^a   Moretti, Robert ^b   Koerner, Mike ^b   Lipshutz, Bruce H ^b  

^a PFIZER INC   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000404899     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00216a045     Document Type: Article

References (12)

1. For recent reviews, see: (a) Lipshutz, B. H. Synthesis 1987, 325. (b) Lipshutz, B. H.; Wilhelm, R. S.; Kozlowski, J. A. Tetrahedron 1984, 40, 5005. (c) Posner, G. H. An Introduction to Synthesis Using Organocopper Reagents; Wiley: NY, 1980. (d) Normant, J. F. Pure Appl. Chem. 1978, 50, 709. (e) J. Organomet. Chem. Lib. 1976, 1, 219. (f) Marino, J. P. Ann. Rep. Med. Chem. 1975, 10, 327. (g) Posner, G. H. Org. React. 1975, 22, 253. (h) Posner, G. H. Org. React. 1972, 19, 1. (i) Jukes, A. E. Adv. Organomet. Chem. 1974, 12, 215.
2. Negishi, E. In Organometallics in Organic Synthesis; Wiley: NY, 1980; Vol. 1. Collman, J.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. In Organotransition Metal Chemistry; University Science Books: Mill Valley, CA, 1987.
3. (a) Lipshutz, B. H.; Kozlowski, J. A.; Breneman, C. M. Tetrahedron Lett. 1985, 26, 5911. (b) Lipshutz, B. H.: Kozlowski, J. A.; Wilhelm, R. S. J. Org. Chem. 1984, 49, 3943.
4. 3SnCl) formed from trisylhydrazones: cf. (a) Pereyre, M.; Quintard, J. P.; Rahm, A. In Tin in Organic Synthesis; Butterworths: London, 1987. (b) Chamberlin, A. R.; Stenke, J. E.; Bond, F. T. J. Org. Chem. 1978, 43, 147.
5. Labadie, J. W.; Stille, J. K. J. Am. Chem. Soc. 1983, 105, 6129.
6. This phenomenon presumably accounts for the limited transferability of acetylene and cyano ligands from copper(I) ate complexes: cf. Corey, E. J.; Beames, D. J. J. Am. Chem. Soc. 1972, 94, 7210. House, H. O.; Umen, M. J. Org. Chem. 1973, 38, 3893. Corey, E. J.; Floyd, D.; Lipshutz, B. H. J. Org. Chem. 1978, 43, 3418. Acker, R. D. Tetrahedron Lett. 1978, 2399. Hamon, L.; Levisalles, J. J. Organomet. Chem. 1983, 251, 133.
7. 2a, bmanner. See, also: Lipshutz, B. H.; Koerner, M.; Parker, D. A. Tetrahedron Lett. 1987. 28, 945.
8. Lipshutz, B. H.; Wilhelm, R. S.; Koslowski, J. A. J. Org. Chem. 1984, 49, 3938. The same selectivity has been noted with lower order reagents: cf. Posner, G. H.; Sterling, J. J.; Whitten, C. E.; Lentz, C. M.; Brunelle, D. J. J. Am. Chem. Soc. 1975, 97, 107.
9. 2. No attempts were made to identify alternate conditions for transmetalations with phenyl-containing cuprates. The reasons for their reduced reactivity toward in situ ligand exchange are unclear at this time but may simply reflect the opportunity for aromatic ring dπ* backbonding with copper(I). (b) Lipshutz, B. H.; Kozlowski, J. A.; Parker, D. A.; Nguyen, S. L.; McCarthy, K. E. J. Organomet. Chem. 1985, 285, 437. (c) Lipshutz, B. H.; Kozlowski, J. A.; Wilhelm, R. S. J. Org. Chem. 1983, 48, 546.
10. A typical procedure for the preparation of misoprostol is as follows: Copper cyanide (1.21 g, 13.5 mmol, flame dried under Argon) in THF (15 mL) was treated with methyllithium (20.6 mL, 1.44 M in diethyl ether, 29.7 mmol) at 0 °C. The cooling bath was removed, and vinylstannane (7.65 g, 15.2 mmol) in THF (15 mL) was added. After 1.5 h at ambient temperature the mixture was cooled to -64 °C (dry ice-isopropyl alcohol), and the enone (3.2 g, 9.63 mmol) in THF (15 mL) was added rapidly via cannula. The temperature rose to -35 °C. After 3 min, the mixture was quenched into a 9:1 saturated ammonium chloride/ammonium hydroxide solution. Ether extraction followed by solvent removal provided 11 g of residue which was solvolyzed (3:1:1, acetic acid, THF, water, 100 mL) and chromatographed (silica gel, EtOAc/hexane eluent) to provide 3.15 g of product (8.2 mmol, 91%) which was identical in all respects with an authentic standard of misoprostol; cf. Collins, P. W., et al. J. Med. Chem. 1977, 20, 1152. This reaction has been successfully carried out on a mole scale in pilot plant equipment.
11. Collins, P. J. Med. Chem. 1986, 29, 437 and references therein.
12. Suzuski, M.; Yanagisawa, A.; Noyori, R. J. Am. Chem. Soc. 1985, 107, 3348.