Selective dihydroxylation of non-conjugated dienes in favor of the terminal olefin

Tetrahedron Letters

Volumn 38, Issue 23, 1997, Pages 4043-4046

  Andrus, Merritt B ^a   Lepore, Salvatore D ^a   Sclafani, Joseph A ^a  

^a PURDUE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; ALKENE; OSMIUM TETRAOXIDE; REAGENT;

ARTICLE; CATALYSIS; CHEMICAL REACTION; DRUG HYDROXYLATION; DRUG SYNTHESIS;

EID: 0030920892     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00861-7     Document Type: Article

References (15)

1. Andrus, M. B.; Lepore, S. D. J. Am. Chem. Soc. 1997, 119, 2327.
2. Brown, H. C.; Bhat, K. S. J. Am. Chem. Soc. 1986, 108, 293
3. Walker, M. A.; Heathcock, C. H. J. Org. Chem. 1991, 56, 5747 and refs. cited therein.
4. (a) Xu, D.; Crispino, G.A.; Sharpless, K.B. J. Am. Chem. Soc. 1992, 114, 7570
5. (b) Becker, H.; Soler, M.A.; Sharpless, K.B. Tetrahedron, 1995, 51, 1345
6. Corey, E. J.; Noe, M. C.; Lin, S. Tetrahedron Lett. 1995, 36, 8741
7. Vidari, G.; Dapiaggi, A.; Zanoni, G.; Garlaschelli, L. Tetrahedron Lett. 1993, 34, 6485
8. Danishefsky, S. J.; Armistead, D. M.; Wincott, F. E.; Selnick, H. G.; Hungate, R. J. Am. Chem. Soc. 1987, 709, 8117
9. Provencal, D. P.; Gardelli, C.; Lafontaine, J. A.; Leahy, J. W. Tetrahedron Lett. 1995, 36, 6033. The substrate diene A, was a tri-substituted olefin with both a benzyloxy and a t-butyldimethylsilyloxy group. (formula presented) Optimal osmylation conditions gave products 5:1 (major/minor) in 73% overall yield. Preliminary reactions with our substrate (table 1, entry 1) proceeded slowly and with low selectivity using these conditions.
10. Use of the AD-mix reagent has been reported for the selective oxidation of a terminal olefin in the presence of a cyclic disubstituted olefin. see: Wipf, P.; Kim, Y.; Goldstein, D. M. J. Am. Chem. Soc. 1995, 117, 11106.
11. Sharpless, K.B.; Amberg, W.; Bennani, Y.L.; Crispino, G.A.; Hartung, J.; Jeong, K.S.; Kwong, H. L.; Morikawa, K.; Wang, Z. M.; Xu, D.; Zang, X. L. J. Org. Chem. 1992, 57, 2768
12. 13C NMR. In addition, select compounds were subject to combustion analysis or high resolution mass spectrometry with satisfactory results. Yields were determined by product isolation after silica gel chromatography.
13. Kolbe, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483 (table 20 and figure 7). Also see: Park, C. Y. Ph. D. Thesis, Massachusetts Institute of Technology, 1991, where allyl alcohols react 23x faster than the coresponding allyl methyl ethers suggestive of a hydrogen bonding effect.
14. Kolbe, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483 (table 20 and figure 7). Also see: Park, C. Y. Ph. D. Thesis, Massachusetts Institute of Technology, 1991, where allyl alcohols react 23x faster than the coresponding allyl methyl ethers suggestive of a hydrogen bonding effect.
15. 1H NMR of the crude periodinate reaction gave a simple spectrum allowing for determination of the dihydroxylation product distribution.