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(broad), J¼8.1 Hz, 2H), 7.48e7.51 (m, 2H); 13C NMR (CDCl3,
400 MHz):
d
3.66 (3H, d, J¼10.3 Hz), 3.70 (3H, d, J¼10.3 Hz), 5.03
100 MHz):
d
6.2 (d, J¼11.0 Hz), 30.4 (d, J¼4.5 Hz), 53.7 (d, J¼7.4 Hz),
(1H, d, J¼10.9 Hz), 7.28e7.37 (3H, m), 7.47e7.48 (2H, m); 13C NMR
54.0 (d, J¼7.6 Hz), 76.9 (d, J¼157.0 Hz), 126.1 (d, J¼4.5 Hz), 127.4 (d,
(CDCl3, 100 MHz):
d
53.5 (d, J¼7.5 Hz), 53.9 (d, J¼6.4 Hz), 70.7 (d,
J¼3.0 Hz), 128.1 (d, J¼2.6 Hz), 138.1; 31P NMR (CDCl3, 161 MHz):
J¼159.1 Hz), 127.1 (d, J¼5.9 Hz), 128.2 (d, J¼2.8 Hz), 128.4 (d,
d
26.23; IR (ATR technique, cmꢁ1): 3283, 2968, 2938, 1220, 1058,
J¼2.1 Hz), 136.5; 31P NMR (CDCl3, 161 MHz):
d 22.92; IR (ATR
1020, 833; HRMS: calculated for C11H17O4P 244.0864 and found
244.0858.
technique, cmꢁ1): 3258, 2956, 1192, 1049, 1023, 774; HRMS: cal-
culated for C9H13O4P 216.0551 and found 216.0547.
4.3.2. Dimethyl 1-hydroxy-1-p-tolylpropylphosphonate(2k). Yield 35%,
crystalline white solid (mp: 114e115 ꢀC); 1H NMR (CDCl3, 400 MHz):
4.4.2. Dimethyl hydroxy(p-tolyl)methylphosphonate (2p). Yield 81%,
crystalline white solid (mp: 102e103 ꢀC); 1H NMR (CDCl3,
d
0.77 (t, J¼7.4 Hz, 3H), 2.11e2.31 (m, 2H), 2.34 (d, J¼1.7 Hz, 3H), 3.05
400 MHz):
d
2.35 (3H, d, J¼1.7 Hz), 3.66 (3H, d, J¼10.3 Hz), 3.71 (3H,
(d, J¼5.8 Hz, 1H), 3.55 (d, J¼10.2 Hz, 3H), 3.74 (d, J¼10.2 Hz, 3H), 7.18
dd, J¼10.3 Hz), 4.16 (1H, dd, J¼8.7 and 5.7 Hz), 4.98 (1H, dd, J¼10.5
(d, J¼8.3 Hz, 2H), 7.45 (dd, J¼8.3, 2.3 Hz, 2H); 13C NMR (CDCl3,
and 5.1 Hz), 7.16 (2H, J¼8.0 Hz), 7.35 (2H, dd, J¼8.0 and 2.1 Hz); 13C
100 MHz):
d
6.1 (d, J¼11.0 Hz), 21.0, 30.1 (d, J¼4.3 Hz), 53.7 (d,
NMR (CDCl3, 100 MHz):
d
21.0, 53.4 (d, J¼7.3 Hz), 53.7 (d, J¼6.7 Hz),
J¼7.6 Hz), 53.9 (d, J¼7.6 Hz), 76.7 (d, J¼157.7 Hz), 126.0 (d, J¼4.6 Hz),
70.1 (d, J¼161.1 Hz), 126.9 (d, J¼6.0 Hz), 128.8 (d, J¼2.2 Hz), 133.5,
128.8 (d, J¼2.4 Hz), 135.1, 136.9 (d, J¼3.3 Hz); 31P NMR (CDCl3,
137.6 (d, J¼3.3 Hz); 31P NMR (CDCl3, 161 MHz):
d 23.91; IR (ATR
161 MHz):
d
26.32; IR (ATR technique, cmꢁ1): 3253, 2977, 2951, 1220,
technique, cmꢁ1): 3258, 2957, 1204, 1046, 1022, 818; HRMS: cal-
culated for C10H15O4P 230.0708 and found 230.0708.
1054, 1022; HRMS: calculated for C12H19O4P 258.1021 and found
258.1014.
4.4.3. Dimethyl hydroxy(4-methoxyphenyl)methylphosphonate (2q).
Yield 80%, crystalline white solid (mp: 94e95 ꢀC); 1H NMR (CDCl3,
4.3.3. Dimethyl 1-(4-fluorophenyl)-1-hydroxypropylphosphonate (2l).
1
Yield 10%, crystalline white solid (mp: 153e155 ꢀC); H NMR (CDCl3,
400 MHz):
s), 4.90 (1H, d, J¼10.2 Hz), 6.81 (2H, d, J¼8.5 Hz), 7.33 (2H, dd, J¼8.5
and 2.1 Hz); 13C NMR (CDCl3, 100 MHz):
d
3.58 (3H, d, J¼10.3 Hz), 3.63 (3H, d, J¼10.3 Hz), 3.73 (3H,
400 MHz):
d
0.77 (d, J¼7.3 Hz, 3H), 2.28e2.09 (m, 2H), 3.0 (d, J¼5.3 Hz,
1H), 3.56 (d, J¼10.2 Hz, 3H), 3.75 (d, J¼10.2 Hz, 3H), 7.04 (t, J¼8.4 Hz,
d
53.5 (d, J¼7.3 Hz), 53.8 (d,
2H), 7.54 (dtd, J¼7.8, 5.3, 2.7 Hz, 2H); 13C NMR (CDCl3, 100 MHz):
d
6.2
J¼7.1 Hz), 55.1, 70.1 (d, J¼162.0 Hz), 113.8 (d, J¼1.5 Hz), 128.4 (d,
(d, J¼10.8 Hz), 30.5 (d, J¼4.9 Hz), 53.8 (d, J¼7.4 Hz), 53.9 (d, J¼7.6 Hz),
76.5 (d, J¼146.9 Hz), 114.9 (dd, J¼21.3, 2.7 Hz), 128.0 (dd, J¼7.8, 4.6 Hz),
134.0 (d, J¼3.2 Hz), 162.2 (d, J¼250.0 Hz); 31P NMR (CDCl3, 161 MHz):
J¼6.2 Hz), 128.5 (d, J¼1.0 Hz), 159.5 (d, J¼1.0 Hz); 31P NMR (CDCl3,
161 MHz): d
24.06; IR (ATR technique, cmꢁ1): 3258, 2956, 1205, 1190,
1047, 1022, 833, 774; HRMS: calculated for C10H15O5P 246.0657 and
found 246.0658.
d
25.96; IR (ATR technique, cmꢁ1): 3246, 2956, 2923, 1507, 1221, 1047,
1012, 812; HRMS: calculated for C11H16FO4P 262.0770 and found
262.0764.
4.4.4. Dimethyl (4-fluorophenyl)(hydroxy)methylphosphonate (2r).
Yield 56%, crystalline white solid (mp: 97e98 ꢀC); 1H NMR (CDCl3,
4.3.4. Dimethyl1-(3-chlorophenyl)-1-hydroxypropylphosphonate(2m).
400 MHz):
d
3.17 (1H, dd, J¼9.2 and 4.6 Hz), 3.69 (3H, d, J¼10.4 Hz),
1
Yield 32%, crystalline white solid (mp: 129e130 ꢀC); H NMR (CDCl3,
3.72 (3H, d, J¼10.4 Hz), 5.03 (1H, dd, J¼10.2 and 3.8 Hz), 7.06 (2H, t,
400 MHz):
d
0.74 (t, J¼7.4 Hz, 3H), 2.13e2.24 (m, 2H), 3.67 (d,
J¼8.4 Hz), 7.45e7.49 (2H, m); 13C NMR (CDCl3, 100 MHz):
d 53.5 (d,
J¼10.3 Hz, 3H), 3.76 (d, J¼10.2 Hz, 3H), 4.16 (d, J¼2.2 Hz,1H), 7.27e7.23
(m, 2H), 7.43 (ddd, J¼7.5, 4.0, 2.0 Hz, 1H), 7.58 (dd, J¼4.0, 2.0 Hz, 1H);
J¼7.4 Hz), 54.0 (d, J¼6.9 Hz), 69.9 (d, J¼161.0 Hz), 115.3 (d, J¼2.3 Hz),
128.8 (d, J¼6.0 Hz), 128.9 (d, J¼6.0 Hz), 132.4, 160.6 (dd, J¼246.6 and
13C NMR (CDCl3, 100 MHz):
d
6.2 (d, J¼11.5 Hz), 30.2 (d, J¼4.1 Hz), 53.8
3.5 Hz); 31P NMR (CDCl3,161 MHz): 23.25; IR (ATR technique, cmꢁ1):
d
(d, J¼7.7 Hz), 54.1 (d, J¼7.7 Hz), 75.7, 124.4 (d, J¼4.2 Hz), 126.6 (d,
3258, 2956, 1205, 1047, 1022, 833, 790; HRMS: calculated for
C9H12FO4P 234.0457 and found 234.0454.
J¼4.6 Hz), 127.4 (d, J¼2.9 Hz), 129.2 (d, J¼2.7 Hz), 134.3 (d, J¼2.7 Hz),
141.0; 31P NMR (CDCl3, 161 MHz):
d
25.42; IR (ATR technique, cmꢁ1):
3241, 2956, 1413, 1223, 1189, 1058, 1026, 777; HRMS: calculated for
C11H16ClO4P 278.0475 and found 278.0471.
4.4.5. Dimethyl (4-chlorophenyl)(hydroxy)methylphosphonate (2s).
Yield 58%, crystalline white solid (mp: 104e105 ꢀC); 1H NMR (CDCl3,
400 MHz):
d
3.63 (3H, d, J¼10.3 Hz), 3.64 (3H, d, J¼10.3 Hz), 4.95 (1H,
4.3.5. Dimethyl 3-hydroxypentan-3-ylphosphonate (2n). Yield 9%,
d, J¼11.0 Hz), 7.25 (2H, d, J¼8.3 Hz), 7.34 (2H, dd, J¼8.3 and 2.2 Hz); 13C
colorless oil; 1H NMR (CDCl3, 400 MHz):
d
0.89 (t, J¼7.5 Hz, 6H),
NMR (CDCl3, 100 MHz):
d
53.6 (d, J¼7.4 Hz), 54.1 (d, J¼7.1 Hz), 69.9 (d,
1.62e1.78 (m, 4H), 2.30 (d, J¼3.7 Hz,1H), 3.74 (d, J¼10.2 Hz, 6H); 13C
J¼160.0 Hz), 128.4 (d, J¼5.8 Hz), 128.5 (d, J¼2.5 Hz), 134.0 (d,
NMR (CDCl3,100 MHz):
d
7.3 (d, J¼5.6 Hz), 27.2 (d, J¼4.8 Hz), 53.2 (d,
J¼3.7 Hz), 135.1 (d, J¼1.2 Hz); 31P NMR (CDCl3, 161 MHz):
d 22.58; IR
J¼5.7 Hz), 75.4 (d, J¼157.3 Hz); 31P NMR (CDCl3, 161 MHz):
d
30.03;
(ATR technique, cmꢁ1): 3258, 2956, 1204, 1191, 1047, 1022, 833, 773;
HRMS: calculated for C9H12 ClO4P 250.0162 and found 250.0158.
IR (ATR technique, cmꢁ1): 3309, 2981, 2955, 1460, 1219, 1027, 823;
HRMS: calculated for C7H17O4P 196.0864 and found 196.0867.
4.4.6. Dimethyl cyclohexanecarbonylphosphonate (2t). Yield 85%,
4.4. General procedure (c)
colorless oil; 1H NMR (CDCl3, 400 MHz):
d 1.04e1.27 (5H, m),
1.58e1.69 (5H, m), 1.93 (1H, d (broad), J¼11.8 Hz), 3.11 (1H, s
To a solution of acyl phosphonate (1 equiv) in dry toluene
(0.5 M) at 0 ꢀC under argon atmosphere was added triethylalumi-
num (3 equiv, 1 M solution in heptane) dropwise. After the com-
pletion of reaction in 10 min, which was monitored by a TLC plate,
the reaction mixture was cautiously hydrolyzed with water. The
reaction mixture was filtrated over Celite and washed with ethyl
acetate. After evaporation of solvent in vacuo, the crude product
was purified by flash column chromatography on silica gel using
ethyl acetate as the eluting solvent.
(broad)), 3.63 (1H, d (broad), J¼5.2 Hz), 3.72 (3H, d, J¼3.0 Hz), 3.75
(3H, d, J¼3.0 Hz); 13C NMR (CDCl3, 100 MHz):
d 26.0, 26.2 (d,
J¼2.7 Hz), 27.8 (d, J¼7.4 Hz), 29.8 (d, J¼8.8 Hz), 39.7 (d, J¼1.9 Hz),
52.9 (d, J¼6.9 Hz), 53.1 (d, J¼7.3 Hz), 72.4 (d, J¼156.0 Hz); 31P NMR
(CDCl3, 161 MHz):
d
25.58; IR (ATR technique, cmꢁ1): 3262, 2923,
2851,1210, 832; HRMS: calculated for C9H19O4P 222.1021 and found
222.1023.
4.4.7. Dimethyl 1-hydroxypropylphosphonate (2u). Yield 48%, col-
orless oil; 1H NMR (CDCl3, 400 MHz):
d
1.02 (3H, t, J¼7.4 Hz),
4.4.1. Dimethyl hydroxy(phenyl)methylphosphonate (2o). Yield 75%,
crystalline white solid (mp: 106e107 ꢀC); 1H NMR (CDCl3,
1.60e1.80 (2H, m), 3.73 (3H, d, J¼10.3 Hz), 3.74 (3H, d, J¼10.3 Hz),
4.46 (1H, dd, J¼6.7 and 2.9 Hz); 13C NMR (CDCl3, 100 MHz):
d 10.3