Asymmetric Dihydroxylation of Dienes: Synthesis of Tetrols

Synlett

Volumn 1996, Issue 1, 1996, Pages 92-94

  Belley, Michel L ^a   Hill, Bryan ^a   Mitenko, Hugh ^a   Scheigetz, John ^a   Zamboni, Robert ^a  

^a MERCK FROSST CENTRE FOR THERAPEUTIC RESEARCH   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0043253810     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1996-5323     Document Type: Article

References (21)

1. For reviews on the AD of alkenes, see a) Kolb, H.C.; Van Nieuwenkze, M.S.; Sharpless; K.B., Chem. Rev., 1994, 94, 2483.
2. b) Johnson, R.A.; Sharpless, K.B. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993, p 227.
3. Lohray, B.B., Tetrahedron: Asymmetry, 1992, 3, 1317.
4. Takahata, H.; Kouno, S.-I.; Momose, T. Tetrahedron: Asymmetry, 1995, 6, 1085.
5. 2 symmetric intermediates in the synthesis of natural products is given by Schreiber, S.L. Chim. Scr., 1987, 27, 563.
6. 1a
7. Crispino, G.A.; Jeong, K-S.; Kolb, H.C.; Wang, Z-M.; Xu, D.; Sharpless, K.B. J. Org. Chem., 1993, 58, 3785.
8. Anderson, P.G.; Sharpless, K.B., J. Am. Chem. Soc., 1993, 115, 7047
9. and Xu, D.; Crispino, G.A.; Sharpless, K.B. J. Am. Chem. Soc., 1992, 114, 7570.
10. 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.; Zhang, X-L. J. Org. Chem., 1992, 57, 2768.
11. 2 or iPrOH:iPrOAc affords the polyols.
12. 2O). Analysis of the NMR spectrum of derivatives confirmed the data shown in the table.
13. Greene, T.W. and Wuts, P.G.M., Protective groups in organic synthesis, 2nd edition; Wiley: New York, 1991.
14. Morikawa, K.; Sharpless, K.B., Tetrahedron Lett. 1993, 34, 5575.
15. Harada, T.; Kurokawa, H.; Kagamihara, Y.; Tanaka, S.; Inoue, A.; Oku, A. J. Org. Chem., 1992, 57, 1412.
16. Burgess, K.; Porte, A.M. Angew. Chem. Int. Ed. Engl., 1994, 33, 1182.
17. 2).
18. The ee of the pure enantiomer 2 can be approximated from the ratio of isomers given in Table 2. If the selectivity of the AD of the first and the second double bond are a:1 and b:1 respectively, the ratio of isomers (2:3:4:5) formed is ab:b:a:1. The ratio obtained by NMR is (ab+1:b:a) divided by a constant k. Solving the equations gave 99% ee and 87% ee respectively for the enantiomers 2j and 5j (obtained from AD of 1j), which is very close to the experimental values.
19. 4-Methyl-1,6-heptadiene was obtained in 18% yield from the addition of allylzinc bromide to ethynylmagnesium bromide. See Bull. Soc. Chim. Fr. 1962, 974 and 1976, 1173 for similar reactions.
20. 2,8-Dimethyl-2,7-nonadiene was prepared in 45% yield by a Wittig reaction between acetone and the bis(phosphosium) salt derivative of 1,5-dibromopentane.
21. 10 (19) 1,8-Nonadien-5-ol was prepared in 74% yield by the addition of (3-buten-1-yl)magnesium bromide to ethyl formate.