H. Inoue et al. / Tetrahedron 58 (2002) 83±90
87
157.5 (d, J4.1 Hz). 31P NMR: 17.8. IR (nujor): 1625 cm21
.
29.7, 43.0, 70.7 (d, J6.2 Hz), 71.5 (d, J6.2 Hz), 74.1,
128.2, 128.4, 128.6, 134.6 (d, J151.0 Hz), 135.3, 143.4
(d, J9.3 Hz). 31P NMR: 19.3. IR (nujor): 3250,
1620 cm21. FABMS m/z: 381 (M1H1). Anal. calcd for
C21H33O4P: C, 66.30;H, 8.74. Found: C, 66.12;H, 8.82.
EIMS m/z: 274 (M1). Anal. calcd for C14H27O3P: C, 61.29;
H, 9.92. Found: C, 61.01;H, 10.12.
3.1.4. Diisopropyl (E)-4-phenyl-1-butenylphosphonate
(2d). A colorless oil. H NMR: 1.25 and 1.33 (each 6H, d,
1
J6.1 Hz, CH3), 2.54 and 2.78 (each 2H, m), 4.59 (2H, m),
5.56 (1H, ddt, J20.4, 17.1, 1.5 Hz, CH), 6.77 (1H, ddt,
J22.0, 17.1, 6.4 Hz, CH), 7.16±7.29 (5H, m, Ph). 13C
NMR: 23.8 (d, J4.1 Hz), 24.0 (d, J4.1 Hz), 33.9, 35.5
(d, J22.8 Hz), 70.0 (d, J4.1 Hz), 119.1 (d, J188.3 Hz),
126.0, 128.2, 128.3, 140.6, 151.3 (d, J4.1 Hz). 31P NMR:
16.5. IR (neat): 1630 cm21. EIMS m/z: 296 (M1). Anal.
calcd for C16H25O3P: C, 64.85;H, 8.50. Found: C, 64.70;
H, 8.68.
3.1.8. Diisopropyl (E)-1-(1-hydroxy-3-phenylpropyl)-2-
phenylethenylphosphonate (5d). Colorless plates of mp
1
64±658C (AcOEt/hexane5:95). H NMR: 1.347, 1.352,
1.38 and 1.41 (each 3H, d, J6.2 Hz, CH3), 1.98 (1H, ddt,
J4.0, 8.2, 13.1 Hz, CH2), 2.32 (1H, m), 2.73±2.85 (2H,
m), 3.84 (1H, d, J10.1 Hz, OH), 4.73 (1H, ddt, J4.0,
10.1, 32.0 Hz, CH), 4.78 (2H, m), 7.07±7.27 (11H, m,
CH, Ph). 13C NMR: 23.4 (d, J4.1 Hz), 23.7 (d,
J4.1 Hz), 23.9 (d, J4.1 Hz), 31.6, 38.4, 67.7 (d,
J6.2 Hz), 70.7 (d, J6.2 Hz), 71.0 (d, J6.2 Hz), 125.5,
128.0, 128.1, 128.2, 128.4, 128.7, 134.6, 134.4, 135.0 (d,
J191.4 Hz), 141.3, 141.7 (d, J8.3 Hz). 31P NMR: 19.0.
IR (nujor): 3350, 1610 cm21. FABMS m/z: 403 (M1H1).
HRMS Anal. calcd for C23H31O4P: C, 68.64;H, 7.76.
Found: C, 68.38;H, 7.86.
3.1.5. Synthesis of diisopropyl (E)-1-(1-hydroxy-2,2-
dimethylpropyl)-2-phenylethenylphosphonate
(5a):
method A. Phosphonate 2a (536 mg, 2.0 mmol) in THF
(5 mL) was added to a solution of LDA (2.4 mmol) in
THF (5 mL) at 2788C. After being stirred for 15 min,
pivalaldehyde (0.3 mL, 2.8 mmol) was added. The mixture
was stirred for 15 min and was quenched with satd NH4Cl,
extracted with EtOAc, washed with brine and dried over
Na2SO4. Concentration and subsequent chromatography
(EtOAc/hexane3:7) gave 5a (R1Ph, R2t-Bu, R3H,
3.1.9. Diisopropyl (E)-1-[hydroxy(phenyl)methyl]-3,3-
dimethyl-1-butenylphosphonate (5e). Colorless plates.
1H NMR: 0.88, 1.14, 1.24 and 1.30 (each 3H, d,
J6.1 Hz, CH3), 1.29 (9H, s, CH3), 4.23 (1H, m), 4.62
(1H, m), 4.85 (1H, d, J11.0 Hz, OH), 6.09 (1H, dd,
J11.0, 34.2 Hz, CH), 6.50 (1H, dd, J0.9, 26.6 Hz, CH),
7.21±7.48 (5H, m, Ph). 13C NMR: 23.35 (d, J3.1 Hz),
23.40 (d, J3.1 Hz), 23.8 (d, J3.1 Hz), 24.1 (d,
J3.1 Hz), 31.1, 34.9 (d, J18.6 Hz), 69.2 (d, J8.3 Hz),
70.4 (d, J6.2 Hz), 71.0 (d, J6.2 Hz), 126.2, 126.8, 127.9,
131.9 (d, J170.7 Hz), 142.3, 154.9 (d, J6.2 Hz). 31P
NMR: 19.7. IR (nujor): 3350, 1620 cm21. FABMS m/z:
355 (M1H1). Anal. calcd for C19H31O4P: C, 64.39;H,
8.82. Found: C, 64.37;H, 9.09.
1
Ri-Pr, 643 mg, 91%) as a colorless oil. H NMR: 0.86
(9H, s, t-Bu), 1.32 and 1.39 (each 3H, d, J6.4 Hz, CH3),
1.40 (6H, d, J6.4 Hz, CH3), 4.66 (1H, dd, J11.0,
33.6 Hz, CH), 4.76 (1H, d, J11.0 Hz, OH), 4.71±4.87
(2H, m), 7.28±7.40 (6H, m, CH, Ph). 13C NMR: 23.4 (d,
J5.2 Hz), 23.80 (d, J5.2 Hz), 23.84 (d, J5.2 Hz), 24.1
(d, J5.2 Hz), 26.5, 37.1, 70.9 (d, J6.2 Hz), 71.3 (d,
J6.2 Hz), 77.2, 128.0, 128.2, 128.5, 136.0, 133.9 (d,
J167.6 Hz), 145.1 (d, J7.2 Hz). 31P NMR: 19.7. IR
(neat): 3400, 1590 cm21. FABMS m/z: 355 (M1H1).
Anal. calcd for C19H31O4P: C, 64.39;H, 8.82. Found: C,
64.64;H, 9.09.
3.1.10. Diisopropyl (E)-1-(1-hydroxy-3-phenylpropyl)-
3,3-dimethyl-1-butenylphosphonate (5f). A pale yellow
oil. H NMR: 1.05 (9H, s, CH3), 1.28, 1.29, 1.33 and 1.36
1
3.1.6. Diisopropyl (E)-1-[hydroxy(phenyl)methyl]-2-
phenylethenylphosphonate (5b). Colorless plates of mp
87±888C (AcOEt/hexane5:95). 1H NMR: 0.98, 1.21,
1.29 and 1.35 (each 3H, d, J6.1 Hz, CH3), 4.36 (1H, m),
4.73 (1H, m), 4.77 (1H, d, J11.0 Hz, OH), 5.96 (1H, dd,
J11.0, 31.4 Hz, CH), 7.22±7.45 (10H, m, Ph), 7.49 (1H, d,
J24.1 Hz, CH). 13C NMR: 23.5 (d, J6.2 Hz), 23.6 (d,
J6.2 Hz), 23.9 (d, J6.2 Hz), 24.1 (d, J5.2 Hz), 70.3
(d, J7.2 Hz), 70.9 (d, J6.2 Hz), 71.4 (d, J6.2 Hz),
126.1, 127.1, 128.1, 128.7, 128.8, 128.9, 134.4 (d,
J172.8 Hz), 134.6, 134.8, 142.2, 142.9 (d, J8.3 Hz).
31P NMR: 18.2. IR (nujor): 3200, 1610 cm21. FABMS
m/z: 375 (M1H1). Anal. calcd for C21H27O4P: C, 67.37;
H, 7.27. Found: C, 67.21;H, 7.15.
(each 3H, d, J6.1 Hz, CH3), 1.81 (1H, m), 2.25 (1H, m),
2.73 (1H, m), 2.89 (1H, m), 4.00 (1H, d, J11.0 Hz, OH),
4.67 (2H, m), 4.78 (1H, ddt, J3.7, 11.0, 34.2 Hz, CH), 6.26
(1H, dd, J0.9, 26.9 Hz, CH), 7.15±7.29 (5H, m, Ph). 13C
NMR: 23.5 (d, J4.1 Hz), 23.9 (d, J4.1 Hz), 24.1 (d,
J4.1 Hz), 30.7, 32.3, 34.4 (d, J19.7 Hz), 39.3, 67.7 (d,
J8.3 Hz), 70.6 (d, J6.2 Hz), 71.0 (d, J6.2 Hz), 125.7,
128.3, 128.7, 133.2 (d, J166.6 Hz), 141.8, 154.3 (d,
J6.2 Hz). 31P NMR: 20.3. IR (nujor): 3400, 1620 cm21
.
FABMS m/z: 383 (M1H1). HRMS calcd for C21H36O4P:
383.2351. Found: 383.2347.
3.1.11. Diisopropyl (E)-2-cyclohexyl-1-(1-hydroxy-3-
phenylpropyl)ethenylphosphonate (5g). A colorless oil.
1H NMR: 1.02±2.18 (11H, m), 1.27, 1.29, 1.32 and 1.34
(each 3H, d, J6.1 Hz, CH3), 1.83 (1H, m), 2.22 (1H, m),
2.76 (2H, m), 3.92 (1H, d, J9.8 Hz, OH), 4.49 (1H, ddt,
J4.9, 9.8, 29.3 Hz, CH), 4.67 (2H, m), 6.13 (1H, dd,
J10.1, 24.4 Hz, CH), 7.15±7.32 (5H, m, Ph). 13C NMR:
23.3 (d, J5.2 Hz), 23.6 (d, J5.2 Hz), 23.7 (d, J5.2 Hz),
23.8 (d, J5.2 Hz), 25.0, 25.4, 31.7, 31.8, 31.9, 37.1 (d,
J16.6 Hz), 39.3, 68.2 (d, J9.3 Hz), 70.2 (d, J6.2 Hz),
70.5 (d, J6.2 Hz), 125.5, 128.0, 128.2, 131.5 (d,
3.1.7. Diisopropyl (E)-1-[cyclohexyl(hydroxy)methyl]-2-
phenylethenylphosphonate (5c). Colorless plates of mp
1
81±828C (AcOEt/hexane5:95). H NMR: 1.35 and 1.41
(each 3H, d, J6.4 Hz, CH3), 1.39 (6H, d, J6.4 Hz, CH3),
0.59±2.23 (11H, m), 3.67 (1H, d, J10.7 Hz, OH), 4.29
(1H, ddd, J10.4, 10.7, 33.9 Hz, CH), 4.80 (2H, m),
7.30±7.39 (5H, m, Ph), 7.37 (1H, d, J24.7 Hz, CH). 13C
NMR: 23.6 (d, J4.1 Hz), 24.0 (d, J4.1 Hz), 24.1 (d,
J4.1 Hz), 24.2 (d, J4.1 Hz), 25.8, 25.9, 26.3, 29.5,