10706
R. Frlan et al. / Tetrahedron 63 (2007) 10698–10708
(25), 71 (30), 57 (34). Anal. Calcd for C20H27O5P: C, 63.48;
H, 7.19. Found: C, 63.31; H, 7.44.
by column chromatography on silica gel using ethyl acetate/
hexane (7/3) as eluant to give a viscous yellow liquid
(344 mg, 75%). H NMR (300 MHz, DMSO-d6) d (ppm):
1
3.12.2. Ethyl 3-(3-methoxyphenoxy)benzyl butylphospho-
nate (7ab). The product was synthesized using the general
procedure described above from methyl 3-(3-methoxyphe-
noxy)phenylmethanol (4ab) (331 mg, 1.44 mmol), ethyl
hydrogen butylphosphonate (358 mg, 2.16 mmol), BOP
(681 mg, 1.54 mmol) and triethylamine (582 mg,
5.76 mmol) in DMF (3 mL). The crude product was purified
by column chromatography on silica gel using ethyl acetate/
hexane (7/3) as eluant to give a viscous orange liquid
0.84 (t, 3H, J¼7.2 Hz, CH3CH2CH2), 1.18 (t, 3H,
J¼7.2 Hz, CH3CH2O), 1.28–1.52 (m, 4H, CH3CH2CH2),
1.65–1.80 (m, 2H, CH2CH2P), 3.65 (s, 3H, CH3O), 3.72
(s, 6H, 2ꢁCH3O), 3.90–4.02 (m, 2H, CH3CH2O), 4.94 (d,
1H, JAB¼13.0 Hz, ArCHAO), 5.02 (d, 1H, JAB¼13.0 Hz,
ArCHBO), 6.38 (s, 2H, 20-H, 60-H), 6.94–6.99 (dd, 1H,
J4/6,5z7.6 Hz, J2,4¼J2,6¼1.9 Hz, 4/6-H), 7.00–7.04 (t, 1H,
J2,4¼J2,6¼1.9 Hz, 2-H), 7.09–7.16 (d, 1H, J¼7.5 Hz, 4/6-
H), 7.34–7.42 (t, 1H, J5,4¼J5,6z7.7 Hz, 5-H); 13C NMR
1
4
(330 mg, 61%). H NMR (300 MHz, DMSO-d6) d (ppm):
(75 MHz, CDCl3) d (ppm): 13.4 (d, JPC¼1.1 Hz), 16.3 (d,
3
2
0.84 (t, 3H, J¼7.2 Hz, CH3CH2CH2), 1.18 (t, 3H, J¼7.0 Hz,
CH3CH2O), 1.27–1.50 (m, 4H, CH3CH2CH2), 1.64–1.80
(m, 2H, CH2CH2P), 3.76 (s, 3H, CH3O), 3.95–4.15 (m, 2H,
CH3CH2O), 4.90 (d, 1H, JAB¼13.0 Hz, ArCHAO), 4.97 (d,
1H, JAB¼13.0 Hz, ArCHBO), 6.57–6.62 (m, 2H, 40/60-HAr,
20-HAr), 6.95–7.10 (m, 3H, HAr), 7.15–7.28 (m, 2H, HAr),
7.32 (t, 1H, J¼7.7 Hz, HAr); 13C NMR (75 MHz, CDCl3)
d (ppm): 13.5, 16.4 (d, 3JPC¼5.9 Hz), 23.6 (d, 3JPC¼17.4 Hz),
24.3 (d, 2JPC¼5.3 Hz), 25.5 (d, 1JPC¼139.4 Hz), 55.3, 61.5 (d,
3JPC¼6.0 Hz), 23.6 (d, JPC¼17.3 Hz), 24.3 (d, JPC
¼
1
5.3 Hz), 25.4 (d, JPC¼139.4 Hz), 56.0, 60.9, 61.5 (d,
2JPC¼6.5 Hz), 66.2 (d, JPC¼6.0 Hz), 97.1, 117.0, 117.7,
2
3
121.9, 129.8, 134.4, 138.6 (d, JPC¼6.2 Hz), 152.6, 153.8,
157.8; 31P NMR (121 MHz, DMSO) d (ppm): 33.9 (s); IR
(NaCl, film): 2958, 1600, 1501, 1447, 1234, 1128, 1008,
784 cmꢂ1; MS (EI): 438 (M+, 100), 273 (85), 149 (24), 69
(20), 55 (30); HRMS: Calcd for C22H31O7P: 438.1807.
Found: 438.1819. Anal. Calcd for C22H31O7Pꢁ0.5H2O:18
C, 59.05; H, 7.21. Found: C, 58.71; H, 7.38.
2
2JPC¼6.7 Hz), 66.3 (d, JPC¼6.2 Hz), 105.1, 109.1, 111.1,
3
117.9, 118.6, 122.3, 129.9, 130.1, 138.7 (d, JPC¼6.2 Hz),
157.3, 158.1, 161.0; 31P NMR (121 MHz, CDCl3) d (ppm):
34.5 (s); IR (NaCl, film): 3460, 2959, 1585, 1488, 1448,
1251, 1154, 1044, 981 cmꢂ1; MS (EI): 378 (M+, 100), 229
(33), 213 (83), 197 (32), 165 (33), 108 (50); HRMS: Calcd
for C20H27O5P: 378.1596. Found: 378.1592. Anal. Calcd for
C20H27O5P$0.5H2O:18 C, 62.01; H, 7.28. Found: C, 62.03;
H, 7.39.
3.12.5. Ethyl 3-(4-benzyloxyphenoxy)benzyl butyl-
phosphonate (7bc). The product was synthesized by the
procedure described above from 3-(4-benzyloxy)phenoxy
benzyl alcohol (4bc) (210 mg, 0.69 mmol), ethyl hydrogen
butylphosphonate (172 mg, 1.03 mmol), BOP (328 mg,
0.74 mmol) and triethylamine (279 mg, 2.76 mmol) in
DMF (2 mL). The crude product was purified by column
chromatography on silica gel using ethyl acetate/hexane
(1/1) as eluant to give viscous yellow liquid (249 mg,
3.12.3. Ethyl 3-(4-methoxyphenoxy)benzyl butylphospho-
nate (7ac). The product was synthesized using general pro-
cedure described above from methyl 3-(4-methoxy)phenoxy
benzyl alcohol (4ac) (282 mg, 1.22 mmol), ethyl hydrogen
butylphosphonate (304 mg, 1.83 mmol), BOP (579 mg,
1.31 mmol) and triethylamine (493 mg, 4.88 mmol) in
DMF (3 mL). The crude product was purified by column
chromatography on silica gel using ethyl acetate/hexane
1
80%). H NMR (300 MHz, CDCl3) d (ppm): 0.89 (t, 3H,
J¼7.4 Hz, CH3CH2CH2), 1.28 (t, 3H, J¼7.2 Hz, CH3CH2O),
1.34–1.46 (m, 2H, CH3CH2CH2), 1.49–1.65 (m, 2H,
CH3CH2CH2), 1.67–1.80 (m, 2H, CH2CH2P), 3.94–4.17
(m, 2H, CH3CH2O), 4.99–5.12 (2ꢁAB system,y 4H, Ar-
CH2), 6.89–6.95 (dd, 1H, J¼8.1, 1.5 Hz, HAr), 6.98 (s, 5H,
CH2Ph), 7.04–7.10 (d, 1H, J¼7.5 Hz, HAr), 7.29–7.49 (m,
6H, HAr); 31P NMR (121 MHz, DMSO-d6) d (ppm): 33.9
(s); IR (NaCl, film): 3412, 2958, 1503, 1242, 1206, 1021,
838 cmꢂ1; MS (FAB): 455 (MH+, 24), 363 (30), 288 (40),
198 (13), 91 (100). Anal. Calcd for C26H31O5Pꢁ1.25H2O:18
C, 65.47; H, 7.08. Found: C, 65.13; H, 6.98.
1
(7/3) to give a viscous orange liquid (303 mg, 66%). H
NMR (300 MHz, DMSO-d6) d (ppm): 0.85 (t, 3H,
J¼7.2 Hz, CH3CH2CH2), 1.17 (t, 3H, J¼7.0 Hz, CH3CH2O),
1.27–1.50 (m, 4H, CH3CH2CH2), 1.64–1.80 (m, 2H,
CH2CH2P), 3.76 (s, 3H, CH3O), 3.85–4.01 (m, 2H,
CH3CH2O), 4.92 (d, 1H, JAB¼13.9 Hz, ArCHAO), 4.98 (d,
1H, JAB¼13.9 Hz, ArCHBO), 6.86–7.05 (m, 6H, HAr),
7.06–7.11 (d, 1H, J4/6,5¼7.9 Hz, 4/6-HAr), 7.32–7.39 (t,
1H, J5,4zJ5,6¼7.9 Hz, 5-HAr); 31P NMR (121 MHz,
DMSO-d6) d (ppm): 33.85 (s); IR (NaCl, film): 3466, 2958,
1505, 1242, 1210, 1029 cmꢂ1; MS (EI): 378 (M+, 94), 213
(45), 167 (100), 139 (76), 103 (55), 87 (74), 74 (50), 61
(44), 55 (55); HRMS: Calcd for C20H27O5P: 378.1596.
Found: 378.1599. Anal. Calcd for C20H27O5Pꢁ0.5H2O:18
C, 62.01; H, 7.28. Found: C, 61.54; H, 7.36.
3.12.6. Ethyl 3-(2-trityloxyphenoxy)benzyl butylphospho-
nate (7ca). The product was synthesized using the general
procedure described above from 3-(2-trityloxy)phenoxy ben-
zyl alcohol (4ca) (150 mg, 0.33 mmol), ethylhydrogen butyl-
phosphonate (823 mg, 0.49 mmol), BOP (155 mg,
0.35 mmol) and triethylamine (133 mg, 1.32 mmol) in
DMF (1 mL). The crude product was purified by column
chromatography on silica gel using ethyl acetate/hexane
(1/1) as eluant to give a viscous yellow liquid (142 mg,
1
72%). H NMR (300 MHz, CDCl3) d (ppm): 0.88 (t, 3H,
3.12.4. Ethyl 3-(3,4,5-trimethoxyphenoxy)benzyl
butylphosphonate (7ad). The product was synthesized by
the procedure described above from methyl 3-(3,4,5-trime-
thoxy)phenoxy benzyl alcohol (4ad) (302 mg, 1.04 mmol),
ethyl hydrogen butylphosphonate (259 mg, 1.56 mmol),
BOP (491 mg, 1.11 mmol) and triethylamine (420 mg,
4.16 mmol) in DMF (2 mL). The crude product was purified
J¼7.4 Hz, CH3CH2CH2), 1.27 (t, 3H, J¼7.2 Hz, CH3CH2O),
1.31–1.47 (m, 2H, CH3CH2CH2), 1.49–1.65 (m, 2H,
CH3CH2CH2), 1.67–1.82 (m, 2H, CH2CH2P), 3.94–4.17
(m, 2H, CH3CH2O), 4.98–5.06 (AB system,y 2H, Ar-CH2),
6.63–6.69 (dd, 1H, J¼8.1, 1.7 Hz, HAr), 6.70–6.75 (dd, 1H,
J¼7.4, 1.7 Hz, HAr), 6.75–6.88 (m, 3H, HAr), 6.90–6.96
(dd, 1H, J¼7.7, 1.7 Hz, HAr), 7.03–7.10 (br d, 1H,