V. A. Petro6 / Tetrahedron Letters 42 (2001) 3267–3269
3269
ganic substrates are easily alkylated in good to moder-
ate yield.
18. Krishnamurti, R.; Bellew, D. R.; Prakash, G. K. S. J.
Org. Chem. 1991, 56, 984–989.
19. The synthesis of silanes is typically carried out on a 0.1
mol scale by addition of the mixture of 1 and chloro-
trimethylsilane to a solution of 2 in 200 mL of diglyme at
−30°C. The crude product removed from the reaction
mixture under vacuum contains silane 4a–d along with
10–15% of RfH and a small amount of chlorosilane. The
product is treated with a solution of sodium thiosulfate,
dried over MgSO4 and distilled. All isolated silanes are
97–99% purity (NMR), contaminated with hexamethyl-
disiloxane. Selected data for compound 4c: bp 90–90.5°C;
1H NMR (CDCl3): 0.34 ppm; 19F NMR: −70.85 (6F, d;
11 Hz), −208.11 (1F, m; 11 Hz); selected data compound
4d: bp 99−100°C; 1H NMR (CDCl3): 0.31 ppm; 19F
NMR: −81.69 (3F, t), −120.43 (2F, m), −126.60 (2F, m),
−129.07 (2F, m). Substrates other than chlorotrimethyl-
silane (typical experiment): mixture of 2 (0.05–0.1 mol)
and an equal volume of the corresponding solvent is
slowly added to a solution of 1a–e (0.06–0.12 mol) and
9b–d (0.05–0.1 mol) in 200 mL of the corresponding
solvent at low temperature (the synthesis of compounds
10a and 10e is carried out by reversed addition of the
mixture of 9a (or 9e) and the corresponding iodide to a
solution of 2). The reaction mixture is kept at the indi-
cated temperature for 1.5–3 h (Table 1), warmed up to
ambient temperature, diluted with an equal volume of
10% HCl, extracted with CH2Cl2 (3×50–100 mL), washed
with 10% HCl (2×100 mL), solution of sodium thiosulfate
(2×100 mL), and dried over MgSO4. The solvent is
removed under vacuum and the crude product distilled.
The ratio of reactants and yields of products are given in
Table 1. Compound 10b: bp 33–34/0.35 mmHg; 1H NMR
(CDCl3): 3.52 (1H, OH), 7.51 (3H, m), 7.80 (2H, m) ppm;
19F NMR: −73.37 (3F, t; 11 Hz), −81.20 (3F, tt; 10, 2.5
Hz), −116.52 (2F, dm, AB pattern; 285 Hz), −119.80 (2F,
dm, AB pattern; 296 Hz), −126.31 (2F, dm, AB pattern;
292 Hz). Anal. calcd for C12H6F12O: C, 36.57; H, 1.53;
found: C, 36.41; H, 1.30.
Acknowledgements
The author thanks Dr. V. Grushin for discussion and
the review for a number of valuable comments. Techni-
cal support by R. Smith, Jr., is also acknowledged.
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