A convenient biphasic process for the monosilylation of symmetrical 1,n- primary diols

Tetrahedron Letters

Volumn 41, Issue 22, 2000, Pages 4281-4285

  Yu, Chengzhi ^a   Liu, Bin ^a   Hu, Longqin ^a  

^a RUTGERS UNIVERSITY   (United States)

Author keywords

1,n diol; Biphasic; Selective protection; Silylation

Indexed keywords

AMINE; HYDROXYL GROUP; N,N DIMETHYLFORMAMIDE;

ARTICLE; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; DERIVATIZATION; NONHUMAN; STOICHIOMETRY; SYNTHESIS;

EID: 0034622022     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(00)00626-2     Document Type: Article

References (26)

1. (a) Nishiguchi, T.; Fujisaki, S.; Ishii, Y.; Yano, Y.; Nishida, A. J. Org. Chem. 1994, 59, 1191-1195;
2. (b) Leznoff, C. C. Acc. Chem. Res. 1978, 11, 327-333;
3. (c) Kata, Y.; Fujiwara, Y.; Asano, Y. Bioorg. Med. Chem. Lett. 1999, 9, 3207-3210.
4. (d) Lalonde, M.; Chan, T. H. Synthesis 1985, 817-845.
5. (a) Raederstorff, D.; Shu, A. Y. L.; Thompson, J. E.; Djerassi, C. J. Org. Chem. 1987, 52, 2337-2346;
6. (b) Kulkarni, B. A.; Chattopadhyay, S.; Chattopadhyay, A.; Mamdapur, V. R. J. Org. Chem. 1993, 58, 5964-5966.
7. (a) Wilkinson, C. G. In Comprehensive Organic Chemistry; Stoddart, J. F., Ed.; Pergamon Press: New York, 1979; Vol. 1, pp. 681-687;
8. (b) Furhop, J.; Penzlin, G. Organic Synthesis; Verlag Chemie: Weinheim, 1983; pp. 143-151;
9. (c) Ogawa, H.; Chihara, T.; Taya, K. J. Am. Chem. Soc. 1985, 107, 1365-1369.
10. (a) Murahashi, S.; Oda, Y.; Naota, T. Chem. Lett. 1992, 2237, and references cited therein;
11. (b) Griffin, B. E.; Jarman, M.; Reese, C. B.; Sulston, J. E. Tetrahedron 1967, 23, 2301-2313;
12. (c) Ortuño, R. M.; Mercé, R.; Font, J. Tetrahedron Lett. 1986, 27, 2519-2522.
13. (a) Terao, O.; Akamatsu, M.; Achiwa, K. Chem. Pharm. Bull. 1991, 39, 823-825;
14. (b) Houille, O.; Schmittberger, T.; Uguen, D. Tetrahedron Lett. 1996, 37, 625-628;
15. (c) Farquhar, D.; Khan, S.; Wilkerson, M. C.; Anderson, B. S. Tetrahedron Lett. 1995, 36, 655-658.
16. McDougal, P. G.; Rico, J. G.; Oh, Y.-I.; Condon, B. D. J. Org. Chem. 1986, 51, 3388-3390.
17. Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; Wiley-Interscience: New York, 1999; Chapter 2, pp. 141-142.
18. 2, rt, 24 h; (e) TBDPSCl (1.05 equiv.), pyridine, rt, 24 h; (f) TBDPSCl (1.05 equiv.), imidazole (5 equiv.), DMF, rt, 24 h; (g) TBDPSCl (1.05 equiv.), NaH (1 equiv.), THF, 0°C-rt, 3 h.
19. Ritchie, C. D.; Lu, S.-Z. J. Am. Chem. Soc. 1989, 111, 8542-8543.
20. In a typical procedure, DIEA (10 mmol, 1.7 mL) and DMF (3 mL) form two immiscible solution phases at room temperature. Using NMR, we found that the top DIEA phase contained about 18% DMF (mol) and the bottom DMF phase contained about 16% DIEA. TLC analysis indicated that reactants used in our experiments were mainly in the bottom DMF phase. We also found that using saturated DIEA solution in DMF as the reaction media decreased both the reaction yield and the selectivity of silylation.
21. Acetone-hexane was found to be a better eluting solvent system than the commonly used ethyl acetate/hexane for the purification and structure assignment of the monosilylated 1,n-primary diols, since ethyl acetate can be strongly retained in compounds containing hydroxyl groups and it is hard to remove completely in vacuo.
22. 2), 1.09 (s, 9H), 1.04 (s, 3H); mono-TBDPS-8: 7.83-7.79 (m, 4H), 7.50-7.45 (m, 4H), 7.33 (br s, 3H), 4.89 (s, 2H), 4.73 (s, 2H), 3.20 (br s, 1H, OH), 1.17 (s, 9H); mono-TBDPS-9: 7.76-7.71 (m, 4H), 7.45-7.41 (m, 6H), 3.73 (t, 2H, J=6.2 Hz), 3.64 (t, 2H, J=5.5 Hz), 2.05 (br s, 1H, OH), 1.68-133 (m, 6H), 1.12 (s, 9H); mono-TBDPS-10: 7.75-7.70 (m, 4H), 7.44-7.41 (m, 6H), 3.71 (t, 2H, J=6.3 Hz), 3.66 (Abq, 2H, Δγ=12.2 Hz, J=6.6 Hz), 1.75 (br s, 1H, OH), 1.61-1.55 (m, 4H), 1.44-1.31 (m, 6H), 1.10 (s, 9H); mono-TBDPS-11: 7.73-7.68 (m, 4H), 7.43-7.39 (m, 6H), 3.69 (t, 2H, J=6.5 Hz), 3.65 (t, 2H, J=6.4 Hz), 1.65-1.50 (m, 4H), 1.48-1.25 (m, 10H), 1.08 (s, 9H).
23. (a) Nicolaou, K. C.; Claiborne, C. F.; Paulvannan, K.; Postema, M. H. D.; Guy, R. K. Chem. Eur. J. 1997, 3, 399-409;
24. (b) Nemoto, H.; Ishibashi, H.; Nagamochi, M.; Fukumoto, K. J. Org. Chem. 1992, 57, 1707-1712; (
25. (c) Feixas, J.; Capdevila, A.; Guerrero, A. Tetrahedron 1994, 50, 8539-8550;
26. (d) Trost, B. M.; Verhoeven, T. R. J. Am. Chem. Soc. 1980, 102, 4743-4763.