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1871
the 1,5-diol (1f) and 1,11-diol (1g), the reaction proceeded
smoothly, and the normal fluorinated compounds were the
major products.
1,10-Bicyclopentane diol also reacted with Deoxo-
FluorTM to give very complicated products based on 13C
and 19F NMR and GC/Mass spectra analysis, but no fluori-
nated ring expansion product was detected. Carrying out the
reaction at reflux in benzene gave a similar result.
system, J = 14.1 Hz), {[4.51 (dd), and 4.64 (dd), 2H, each
split by JHF = 47.7 Hz], ABX pattern, JAB = 9.8 Hz, JAX
=
5.3 Hz, JBX = 3.2 Hz}, 7.12–7.32 (m, 15H). 13C NMR d
30.95 (d, J = 6.0 Hz), 55.33 (d, J = 2.0 Hz), 60.12 (d, J =
17.4 Hz), 84.42 (d, J = 171.5 Hz), 127.00, 127.74, 129.09,
129.22, 129.45, 130.23, 140.19, 140.80. 19F NMR d
ꢀ226.23 (td, 1F, J = 47.7 Hz, J = 25.2 Hz). MS (EI) m/z
(species, rel. int.): 333 (M+, 0.2), 300 [M+ ꢀ CH2F, 0.4], 242
+
(M+ ꢀ C6H5CH2, 22), 210 (C6H5CH2)2NCH2 , 22), 91
+
(C6H5CH2 , 100).
3. Conclusions
4.2.2. 3a
When 2-amino alcohols and 1,2-diols were treated with
Deoxo-FluorTM in methylene chloride, the rearranged com-
pounds were isolated as the major products concomitantly
with the normal replacement products in good yields.
Yield, 71%. 1H NMR d 2.75–2.96 (m, 4H), 3.74 (s, 4H),
1
4.78–5.01 (broad d, H), 7.19–7.44 (m, 15H).13C NMR d
40.66 (d, J = 21.0 Hz), 57.53 (d, J = 21.9 Hz), 60.01 (d, J =
1.5 Hz), 94.43 (d, J = 171.8 Hz), 127.38, 127.94, 129.20,
129.31, 129.84, 130.18, 138.30 (d, J = 3.8 Hz), 140.20. 19
F
NMR d ꢀ179.89 (m, 1F). MS (EI) m/z (species, rel. int.): 333
(M+, 0.5), 210 ((C6H5CH2)2NCH2 , 22), 91 (C6H5CH2 ,
100). HRMS: C23H24FN, Calcd. 333.1893; Found:
333.1891.
+
+
4. Experimental
4.1. General
The amino alcohols, diols and Deoxo-FluorTM were
purchased from Aldrich and used as received. 1H, 19F,
and 13C NMR spectra were recorded in CDCl3 on a Bruker
300 spectrometer. Chemical shifts are reported in ppm
relative to the appropriate standard, CFCl3 for 19F, and
TMS for 1H and 13C NMR spectra. GC/MS was performed
on a Shimadzu GC/MSQP5050 spectrometer. HRMS were
obtained using a JEOL JMS-AX505HA spectrometer.
4.2.3. 2b
1
Yield, 7%. H NMR d 1.13 (dd. 3H, J = 6.9 Hz, J =
1.5 Hz), 3.65 and 3.76 (2 ꢁ d, 2 ꢁ 2H, AB system, J =
14.0 Hz), {3.05–3.15 (broad d), [4.43 (dd), and 4.50 (dd),
2H, each split by JHF = 47.8 Hz], ABX pattern, JAB = 9.4 Hz,
J
AX = 6.2 Hz, JBX = 5.1 Hz}, 7.24–7.42 (m, 10H). 13C NMR
d 11.67 (d, J = 6.2 Hz), 53.46 (d, J = 18.7 Hz), 55.03 (d, J =
1.4 Hz), 86.53 (d, J = 170.9 Hz), 127.70, 129.09, 129.38,
141.10. 19F NMR d ꢀ226.23 (td, 1F, J = 47.8 Hz, J =
19.6 Hz). MS (EI) m/z (species, rel. int.): 257 (M+, 1.3),
224 [M+ ꢀ CH2F, 0.43], 242 (M+ ꢀ C6H5CH2, 37), 210
4.2. General procedure for the reaction of 2-amino
alcohols and diols with Deoxo-FluorTM
+
+
((C6H5CH2)2NCH2 , 7), 91 (C6H5CH2 , 100).
To a stirred solution of amino alcohol or diol (4 mmol)
in dichloromethane (10 ml) at 0 8C, Deoxo-FluorTM
(4.4 mmol for amino alcohols and 9 mmol for diols)
was added dropwise as a neat liquid. After 10 min, the
cold bath was removed and the reaction mixture was
stirred at room temperature for 1–5 h. The progress of
the reaction was monitored by TLC. Upon completion, the
reaction was worked up by cooling and slowly adding
sodium bicarbonate solution followed by washing with
water. The product was purified by rotary thin layer
chromatography on silica gel in hexane/dichloromethane.
In the case of 1g, the aqueous solution was extracted with
diethyl ether which afforded the compound 2g. For 1f, the
reaction was performed under neat conditions at 25 8C.
After stirring for 5 h, the mixture was distilled under
vacuum and it was trapped with liquid nitrogen at
ꢀ196 8C to give 2f.
4.2.4. 3b
1
Yield, 82%. H NMR d 1.32 (dd. 3H, J = 23.8 Hz, J =
6.3 Hz), {[2.65 (dd, 1H), each split by JHF = 25.8 Hz], [2.78
1
(dd, H), each split by JHF = 18.3 Hz], 4.76–5.02(broad d,
1H), ABX pattern, JAB = 14.0 Hz, JAX = 6.6 Hz, JBX
=
4.0 Hz}, 3.74 (s, 4H), 7.30–7.47 (m, 10H). 13C NMR d 20.18
(d, J = 22.1 Hz), 59.26 (d, J = 21.5 Hz), 59.99 (d, J = 1.6 Hz),
90.81 (d, J = 165.5 Hz), 127.88, 129.15, 129.74, 140.39. 19
F
NMR d ꢀ174.40 (m, 1F). MS (EI) m/z (species, rel. int.): 257
(M+, 0.7), 237 [M+ ꢀ HF, 0.3], 210 (C6H5CH2)2NCH2 , 7),
+
+
91 (C6H5CH2 , 100). HRMS: C17H20FN, Calcd. 257.1580;
Found: 257.1572.
4.2.5. 2c/3c
Yield 86%. 2c 19F NMR d ꢀ220.87 (td, 1F, J = 47.6 Hz,
J = 14.0 Hz). MS (EI) m/z (species, rel. int.): 193 (M+, 5),
160 [M+ꢀ CH2F, 85], 91 (C6H5CH2 , 100). 3c 19F NMR d
+
4.2.1. 2a
ꢀ180.53 (m, 1F). MS (EI) m/z (species, rel. int.): 193
(M+, 58), 192 (M+ꢀ H, 55), 173 (M+ ꢀ HF, 5), 116
Yield, 15%. 1H NMR d{[2.85 (ddd) and 3.02 (ddd), 2H],
(M+ ꢀ C6H5, 90), 102 (M+ ꢀ benzyl, 81), 91 (C6H5CH2 ,
+
3.05–3.24 (broad d), ABX pattern, JAB = 13.4 Hz, JAX
=
8.4 Hz, JBX = 6.3 Hz}, 3.80 and 3.85 (2 ꢁ d, 2 ꢁ 2H, AB
100).