1262 Bull. Chem. Soc. Jpn. Vol. 79, No. 8 (2006)
Synthesis of Ethers
0.76 (m, 9H), 0.65 (d, J ¼ 6:9 Hz, 3H); 13C NMR (68 MHz,
CDCl3) ꢀ 132.7 (d, J ¼ 3:4 Hz), 132.6 (d, J ¼ 2:8 Hz), 132.1 (d,
J ¼ 11:2 Hz), 131.9 (d, J ¼ 11:2 Hz), 129.0 (d, J ¼ 137:5 Hz),
128.4 (d, J ¼ 139:7 Hz), 128.4 (d, J ¼ 14:0 Hz), 128.3 (d, J ¼
14:0 Hz), 81.0 (d, J ¼ 8:9 Hz), 48.8 (d, J ¼ 7:3 Hz), 43.8 (d,
J ¼ 1:1 Hz), 33.8, 31.5, 25.6, 22.6, 21.9, 21.1, 15.4; HRMS
(APCIþ) calcd for C23H33NO3PS ½M þ Hꢃþ 434.1919, found
m=z 434.1907.
10H), 4.56 (d, J ¼ 11:2 Hz, 1H), 4.41 (d, J ¼ 11:2 Hz, 1H), 3.74
(s, 3H), 1.88 (s, 3H); 13C NMR (68 MHz, CDCl3) ꢀ 173.4, 141.0,
138.3, 128.3, 128.2, 127.9, 127.3 (ꢄ2), 125.7, 81.9, 66.8, 52.5,
23.6; HRMS (GC-EIþ) calcd for C17H19O3 ½M þ Hꢃþ 271.1334,
found m=z 271.1320.
Methyl 3-O-Allyl-2-O-benzoyl-4,6-di-O-benzylidene-ꢀ-D-
20
glucopyranoside (9):
Colorless oil; ½ꢁꢃD þ124:4 (c 0.35,
CHCl3); IR (ATR, cmꢂ1) 2933, 1720, 1452, 1375, 1269, 1092,
1048, 991, 922, 710, 699; 1H NMR (270 MHz, CDCl3) ꢀ 8.10
(d, J ¼ 7:1 Hz, 2H), 7.62–7.36 (m, 8H), 5.91–5.77 (m, 1H), 5.60
(s, 1H), 5.21 (d, J ¼ 15:7 Hz, 1H), 5.10–5.05 (m, 3H), 4.38–4.07
(m, 4H), 3.98–3.61 (m, 3H), 3.38 (s, 3H); 13C NMR (68 MHz,
CDCl3) ꢀ 165.8, 137.2, 134.7, 133.1, 129.7, 129.6, 128.8, 128.3,
128.1, 125.9, 116.9, 101.2, 97.8, 81.9, 75.6, 73.8, 73.5, 68.9, 62.3,
55.4; HRMS (APCIþ) calcd for C24H27O7 ½M þ Hꢃþ 427.1757,
found m=z 427.1753.
Typical Experimental Procedure for Preparation of Ethers
by the Alkylation of Alcohols Using Alkyl N-(Methylsulfonyl)-
diphenylphosphinimidate (Table 3). To a stirred solution of al-
kyl N-(methylsulfonyl)diphenylphosphinimidate (0.3 mmol) and
alcohol (0.3 mmol) in 1,2-dimethoxyethane (0.48 mL) under an
argon atmosphere was added a solution of Me3SiOTf (0.03 mmol)
in 1,2-dimethoxyethane (0.02 mL) at 0 ꢁC. The reaction mixture
was stirred at room temperature. After completion of the reaction
(detected by TLC), the mixture was quenched with saturated
NaHCO3 and was extracted with ethyl ether. The organic layers
were dried over anhydrous sodium sulfate, then filtered and con-
centrated. The crude product thus obtained was purified by prep-
arative TLC to give the corresponding ether.
1-Methyl-3-phenylpropyl Phenethyl Ether (10): Colorless
oil; IR (ATR, cmꢂ1) 3026, 2927, 2864, 1603, 1494, 1453, 1373,
1
1341, 1135, 1095, 1078, 1030, 906, 745, 696, 574, 476; H NMR
(270 MHz, CDCl3) ꢀ 7.32–7.09 (m, 10H), 3.77–3.69 (m, 1H),
3.55–3.47 (m, 1H), 3.42–3.31 (m, 1H), 2.88 (t, J ¼ 7:3 Hz, 2H),
2.72–2.52 (m, 2H), 1.90–1.59 (m, 2H), 1.15 (d, J ¼ 6:2 Hz, 3H);
13C NMR (68 MHz, CDCl3) ꢀ 142.2, 139.1, 128.9, 128.3, 128.2,
128.1, 126.0, 125.5, 74.6, 69.5, 38.5, 36.9, 31.8, 19.7; HRMS
(APCIþ) calcd for C18H23O ½M þ Hꢃþ 255.1749, found m=z
255.1756.
Benzyl Phenethyl Ether (4):17 Colorless oil; IR (ATR, cmꢂ1
)
2856, 1098, 734; 1H NMR (270 MHz, CDCl3) ꢀ 7.31–7.20 (m,
10H), 4.52 (s, 2H), 3.69 (t, J ¼ 7:2 Hz, 2H), 2.93 (t, J ¼ 7:2 Hz,
2H); 13C NMR (68 MHz, CDCl3) ꢀ 138.8, 138.2, 128.8, 128.2,
128.2, 127.5, 127.4, 126.1, 72.9, 71.2, 36.4; HRMS (GC-EIþ)
calcd for C15H16O [M]þ 212.1296, found m=z 212.1194.
Benzyl 1-Methyl-3-phenyl Ether (5):18 Colorless oil; IR
(ATR, cmꢂ1) 3062, 3026, 2967, 2927, 2860, 1495, 1453, 1373,
1133, 1090, 1064, 1028, 732, 695; 1H NMR (270 MHz, CDCl3)
ꢀ 7.35–7.14 (m, 10H), 4.57 (d, J ¼ 12:0 Hz, 1H), 4.43 (d, J ¼
12:0 Hz, 1H), 3.58–3.47 (m, 1H), 2.82–2.60 (m, 2H), 2.00–1.67
(m, 2H), 1.22 (d, J ¼ 6:1 Hz, 3H); 13C NMR (68 MHz, CDCl3)
ꢀ 142.2, 138.9, 128.3, 128.2, 128.2, 127.5, 127.3, 125.6, 74.1,
70.3, 38.5, 31.9, 19.7; HRMS (APCIþ) calcd for C17H21O ½M þ
Hꢃþ 241.1592, found m=z 241.1596.
Benzyl Phenethyloxy-2-phenylacetate (11): Colorless oil;
IR (ATR, cmꢂ1) 3030, 2869, 1747, 1453, 1166, 1115, 730, 695;
1H NMR (270 MHz, CDCl3) ꢀ 7.43–7.14 (m, 15H), 5.15 (d, J ¼
12:4 Hz, 1H), 5.09 (d, J ¼ 12:4 Hz, 1H), 4.91 (s, 1H), 3.79–3.58
(m, 2H), 3.05–2.88 (m, 2H); 13C NMR (68 MHz, CDCl3) ꢀ 170.4,
138.2, 136.2, 135.3, 128.8, 128.5, 128.4, 128.3, 128.2, 128.1,
127.8, 127.0, 126.1, 81.1, 70.7, 66.7, 36.2; HRMS (APCIþ) calcd
for C23H23O3 ½M þ Hꢃþ 347.1647, found m=z 347.1639.
Phenethyl 1-Phenylethyl Ether (12): Colorless oil; IR (ATR,
1
cmꢂ1) 2860, 1495, 1452, 1101, 752; H NMR (270 MHz, CDCl3)
26
Ethyl (S)-2-Benzyloxypropanoate (6):19 Colorless oil; ½ꢁꢃD
ꢀ 7.31–7.16 (m, 10H), 4.40 (q, J ¼ 6:5 Hz, 1H), 3.51 (t, J ¼ 7:4
Hz, 2H), 2.91 (dt, J ¼ 7:4 Hz, J ¼ 13:7 Hz, 1H), 2.84 (dt, J ¼
7:4 Hz, J ¼ 13:7 Hz, 1H), 1.43 (t, J ¼ 6:5 Hz, 3H); 13C NMR (68
MHz, CDCl3) ꢀ 143.8, 138.9, 128.8, 128.3, 128.3, 128.1, 127.2,
126.0, 78.1, 69.6, 36.6, 24.2; HRMS (GC-EIþ) calcd for C16H18O
[M]þ 226.1358, found m=z 226.1352.
20
ꢂ83:0 (c 0.99, CHCl3), [lit.19 ½ꢁꢃD ꢂ80:9 (c 7.15, AcOEt)]; IR
(ATR, cmꢂ1) 2984, 2938, 1743, 1453, 1372, 1269, 1197, 1139,
1
1115, 1064, 1023, 738, 697; H NMR (270 MHz, CDCl3) ꢀ 7.36–
7.25 (m, 5H), 4.70 (d, J ¼ 11:6 Hz, 1H), 4.45 (d, J ¼ 11:3 Hz,
1H), 4.27–4.15 (m, 2H), 4.05 (q, J ¼ 6:8 Hz, 1H), 1.44 (d, J ¼
6:8 Hz, 3H), 1.29 (t, J ¼ 7:0 Hz, 3H); 13C NMR (68 MHz, CDCl3)
ꢀ 173.0, 137.4, 128.3, 127.8, 127.7, 74.0, 71.9, 60.8, 18.8, 14.3;
HRMS (APCIþ) calcd for C12H17O3 ½M þ Hꢃþ 209.1178, found
m=z 209.1175.
1,1-Dimethyl-3-phenylpropyl 1-Phenethyl Ether (13): Col-
orless oil; IR (ATR, cmꢂ1) 3026, 2971, 2927, 1603, 1493, 1452,
1
1382, 1366, 1203, 1080, 1027, 957, 759, 739, 697; H NMR (270
MHz, CDCl3) ꢀ 7.38–7.05 (m, 10H), 4.66 (q, J ¼ 6:5 Hz, 1H),
2.75–2.52 (m, 2H), 1.87–1.66 (m, 2H), 1.39 (d, J ¼ 6:5 Hz, 3H),
1.17 (s, 3H), 1.14 (s, 3H); 13C NMR (68 MHz, CDCl3) ꢀ 147.3,
142.8, 128.2, 128.1, 128.0, 126.4, 125.5, 125.4, 75.8, 69.7, 43.5,
30.6, 26.9, 26.5; Anal. calcd for C19H24O: C, 85.03; H, 9.01%;
Found: C, 84.81; H, 9.21%.
Methyl 2-O-Benzoyl-3-O-benzyl-4,6-di-O-benzylidene-ꢀ-D-
20
glucopyranoside (7):20 Colorless oil; ½ꢁꢃD þ130:1 (c 1.05,
CHCl3), [lit.20 ½ꢁꢃD þ135 (c 1.0, CHCl3)]; IR (ATR, cmꢂ1
)
2931, 2859, 1727, 1453, 1368, 1268, 1090, 1043, 998, 713, 699;
1H NMR (270 MHz, CDCl3) ꢀ 8.06–8.03 (m, 2H), 7.62–7.38
(m, 8H), 7.26–7.17 (m, 5H), 5.62 (s, 1H), 5.14–5.06 (m, 2H),
4.88 (d, J ¼ 11:9 Hz, 1H), 4.77 (d, J ¼ 11:9 Hz, 1H), 4.34 (dd,
J ¼ 4:1 Hz, J ¼ 9:7 Hz, 1H), 4.20 (t, J ¼ 9:4 Hz, 1H), 3.97–3.76
(m, 3H), 3.37 (s, 3H); 13C NMR (68 MHz, CDCl3) ꢀ 165.8, 138.1,
137.2, 133.2, 129.8, 129.5, 128.9, 128.3, 128.2, 128.1, 127.8,
127.5, 125.9, 101.3, 97.8, 82.2, 75.7, 74.7, 73.5, 69.0, 62.3, 55.4;
HRMS (APCIþ) calcd for C28H29O7 ½M þ Hꢃþ 477.1913, found
m=z 477.1924.
N-(Methylsulfonyl)diphenylphosphinamide (19): Isolated
as a white solid; mp 249–250 ꢁC; IR (ATR, cmꢂ1) 2886, 2742,
1
2610, 1385, 1314, 1182, 1152, 902, 692, 534, 504, 439; H NMR
(270 MHz, DMSO) ꢀ 7.86–7.73 (m, 4H), 7.62–7.48 (m, 6H), 3.18
(s, 3H); 13C NMR (68 MHz, DMSO) ꢀ 132.0 (d, J ¼ 2:8 Hz),
131.9 (d, J ¼ 127:4 Hz), 131.2 (d, J ¼ 10:6 Hz), 128.4 (d, J ¼
12:9 Hz), 44.4; HRMS (APCIþ) calcd for C13H15NO3PS ½M þ
Hꢃþ 296.0510, found m=z 296.0507.
Methyl 2-Benzyloxy-2-phenylpropanoate (8):21 Colorless
oil; IR (ATR, cmꢂ1) 3029, 2949, 1732, 1449, 1253, 1113, 1074,
1027, 732, 696; 1H NMR (270 MHz, CDCl3) ꢀ 7.55–7.24 (m,
1,1-Dimethyl-3-phenypropyl N-(Diphenoxyphosphoryl)di-
phenylphosphinimidate (3m). To a stirred solution of 1b
(348.4 mg, 1.00 mmol) in THF (1.0 mL) under an argon atmo-