1154
S. Stavber et al.
LETTER
mmol of N-F reagent 1 were added and the reaction mixture
stirred at 55 C until KI starch paper showed the consumption
of the reagents. The solvent was removed under reduced
presure and the crude reaction mixture dissolved in 100 mL of
CH2Cl2, insoluble material filtered off, the solution washed
with water (2 50 mL), dried over anhydrous Na2SO4, and
the solvent evaporated. The isolated crude reaction mixtures
were analysed by 1H NMR and TLC, amounts of products 3a-
f and 5a-b determined by an internal standard and the pure
compounds obtained after flash chromatography over SiO2.
1H NMR, IR and MS data validated the claimed structures,
while the purities of all new compounds were confirmed by
elemental analysis.
Reaction of HMB with N-F regents 1 in the presence of
cyanides
To a solution of 5 mmol of HMB in TFA (50 mL) 15 mmol of
corresponding cyanide and 5 mmol of N-F reagent 1 were
added and the reaction mixture stirred at 55 C until KI starch
paper showed the consumption of the reagents. The solvent
was removed under reduced pressure and the crude reaction
mixture dissolved in 100 mL of CH2Cl2, insoluble material
filtered off, the solution washed with 1% aqueous KOH (50
mL) and water (50 mL), dried over anhydrous Na2SO4, and the
solvent evaporated to half its volume. The products were
precipitated from this solution by n-hexane, filtered off and
dried. The precipitated crude products were analysed by 1H
NMR and TLC, amounts of compounds 4a-j determined by
internal standard and pure compounds obtained after
crystallisation from n-hexane/acetone. 1H NMR, IR and MS
data validated the claimed structures, while the purities of all
new compounds were confirmed by elemental analysis.
(8) R. Bishop, “Ritter-type Reactions” in Comprehensive Organic
Synthesis, Vol 6., Eds. B. M. Trost, I. Fleming and E.
Winterfeld, Pergam Press, Oxford, 1991.
Scheme 2
References and Notes
(9) Suzuki, H.; Nakamura, K. Bull. Chem. Soc. Jpn. 1968, 41,
2197.
(1) a) Lal, G. S.; Pez, G. P.; Syvret, R.G. Chem. Rev. 1996, 96,
1737; b) Taylor, S. D.; Kotoris, C. C.; Hum, G. Tetrahedron
1999, 55, 12431; c) Furin G. G.; Fainzilberg, A. A. Russian
Chem. Rev. 1999, 68, 653.
(2) a) Baasner, B.; Hagemann, H.; Tatlow, J. C. Eds., Methods of
Organic Chemistry (Houben-Weyl) Vol. E 10a and 10b:
Organofluorine Compounds, Thieme, New York, 1999.
(3) a) Gilicinski, A.G.; Pez, G.P.; Syvret, R.G.; Lal, G.S. J.
Fluorine Chem. 1992, 59, 157; b) Differding, E.; Bersier, P.M.
Tetrahedron 1992, 48, 1595.
(10) 3-[(Pentamethylbenzyl)oxy]propanenitrile (9):
white crystals; mp 65.7-66.2 °C; 1H NMR: = 2.27(s, 6H),
2.35(s, 9H), 2.60(t, J = 6 Hz, 2H), 3.77(t, J = 6 Hz, 2H),
4.70(s, 2H); IR: CN = 2220 cm-1, COC = 1075 cm-1; MS m/z:
231(M+, 20%), 216(8), 161(62), 160(100), 147(20), 145(25),
91(25); anal. calcd. for C15H21NO: C 77.88, H 9.15, N 6.05;
found C 78.29, H 8.92, N 5.96.
(11) 3-Oxo-3-[(pentamethylbenzyl)amino]propyl trifluoro
acetate (10):
white crystals; mp 184-185 °C; 1H NMR: = 2.30(s, 15H),
2.53(t, J = 5 Hz, 2H), 4.50(t, J = 5 Hz, 2H), 4.60(d, J = 5 Hz,
2H), 5.40(broad s, 1H); 19F NMR: = -76.0(s); IR: : 3272,
1780, 1620, 1525, 1220, 1150 cm-1,; MS m/z: 345(M+, 24%),
330(13), 161(34), 160(100), 147(25), 145(20); anal. calcd. for
C17H22F3NO3: C 59.12, H 6.42, N 4.06; found C 59.28, H 6.54,
N 4.04.
(4) a)Visser, G.W.M.; Bakker, C.N.M.; vHalteren, B.W.;
Herscheid, D.M.; Brinkman, G.A.; Hoekstra, A. J. Org.
Chem. 1986, 51, 1886; b) Stavber, S.; Zupan, M. J. Org.
Chem. 1991, 56, 7347.
(5) a) Zupan, M. Chimia 1976, 30, 305; b) Šket, B.; Zupan. M. J.
Org. Chem. 1978, 43, 835; c) Stavber, S.; Zupan, M. J. Org.
Chem. 1983, 48, 2223.
(6) a) Singh, S.; DesMarteau, D.D.; Zuberi, S.S.; Witz, M.;
Huang, H.N. J. Am. Chem. Soc. 1987, 109, 7194; b) Lal; G.S.
J. Org. Chem. 1993, 58, 2791.
(12) a) Eberson, L.; Helgee, B. Acta Chem. Scan. B 1978, 32, 157;
b) Bewick, A.; Edwards, G.J.; Mellor, J.M. Liebigs Ann.
Chem. 1978, 41.
(7) 1-Fluoro-4-chloromethyl-1,4-diazoniabicyclo 2.2.2 octane
bis(tetrafluoroborate) (1a, SelectfluorTM F-TEDA-BF4) from
Apollo,1-Fluoro-4-hydroxy-1,4-diazoniabicyclo 2.2.2 octane
bis(tetrafluoroborate) (1b, AccufluorTM NFTh as 50% mixture
with Al2O3) and N-Fluorobenzenesulfonimide (1c, NFSi)
from AlliedSignal Inc., N-Fluoro-2,6-dichloropyridinium
tetrafluoroborate (1d, FP-B800) from Chichibu Onoda
Cement Corp., and HMB from Aldrich were used.
Reaction of HMB with N-F regents 1 in the presence of
alcohols or TMS-R
(13) Wasserman, H.; Mariano, P.S.; Keehn, P.M. J. Org. Chem.
1971, 36, 1765.
(14) Dalla Cort, A.; Mandolini, L.; Panaioli, S. Synth. Commun.
1988, 18, 613.
(15) a) Dalla Cort, A.; La Barbara, A.; Mandolini, L. J. Chem. Res.
(S) 1983, 44; b) Maini, S.; Mandolini, L.; Rol, C. J. Org.
Chem. 1978, 43, 3236.
(16) Lau, W.; Kochi, J.K. J. Org. Chem. 1984, 106, 6720.
To a solution of 5 mmol of HMB in MeCN (50 mL) 25 mmol
of corresponding alcohol or TMS derivative (Table) and 5
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Synlett 2001, No. 7, 1152–1154 ISSN 0936-5214 © Thieme Stuttgart · New York