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M. A. Brimble et al.
PAPER
MS (EI, 70 eV): m/z (%) = 486 (14, [M]+), 395 (1), 378 (1), 320 (1),
290 (2.5), 256 (1.5), 230 (4), 199 (3.5), 179 (4.5), 165 (2), 149 (4),
139 (4.5), 121 (3), 91 (100), 65 (5.5), 57 (6), 55 (4), 43 (4.5).
MS (EI, 70 eV): m/z (%) = 286 (28.5, [M]+), 177 (24), 147 (100),
121 (5), 107 (3), 95 (6.5), 91 (5), 80 (4.5), 77 (4.5), 65 (2), 57 (4),
52 (7), 39 (11).
HRMS (EI): m/z [M]+ calcd for C30H30O6: 486.2042; found:
HRMS (EI): m/z [M]+ calcd for C16H14O5: 286.0841; found:
486.2039.
286.0844.
1-[2-(Benzyloxy)-3-methoxyphenoxy]-3-[2-(benzyloxy)phen-
oxy]propan-2-one (17)
Ketone 17 was prepared as described above for ketone 16, from re-
action of TPAP (30 mg, 0.085 mmol) and NMO (102 mg, 0.867
mmol) with alcohol 34 (211 mg, 0.434 mmol) in anhyd CH2Cl2 (1
mL) containing activated 4 Å MS (100 mg) at r.t. for 2 h; yield: 180
mg (86%); colorless solid; mp 73–75 °C.
1-[2-(Benzyloxy)-3-methoxyphenoxy]-3-[3-(benzyloxy)naph-
thalen-2-yloxy]propan-2-ol (35)
Alcohol 35 was prepared as described above for alcohol 31, from re-
action of K2CO3 (65 mg, 0.47 mmol) and epoxide 23 (72 mg, 0.24
mmol) in acetone (5 mL) with phenol 22 (54 mg, 0.24 mmol) in
acetone (3 mL) at 110 °C for 38 h; yield: 108 mg (86%); viscous
yellow oil.
IR (film): 3066, 3033, 2937, 1744, 1595, 1499, 1476, 1454, 1377,
1257, 1117 cm–1.
IR (film): 3462, 3062, 3032, 2938, 1599, 1508, 1477, 1256, 1173,
1112 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.81 (s, 3 H, OCH3), 4.81 (s, 2 H,
C-3¢¢¢–OCH2), 4.84 (s, 2 H, C-1¢–OCH2), 5.03 (s, 2 H, C-2¢–
OCH2Ph), 5.08 (s, 2 H, C-2¢¢¢–OCH2Ph), 6.41 (dd, J = 8.4, 1.2 Hz,
1 H, 4¢-H or 6¢-H), 6.61 (dd, J = 8.4, 1.1 Hz, 1 H, 4¢-H or 6¢-H),
6.79–6.98 (m, 5 H, 5¢-H, 3¢¢¢-H, 4¢¢¢-H, 5¢¢¢-H and 6¢¢¢-H), 7.21–7.34
(m, 6 H, 3¢¢-H, 3¢¢¢¢-H, 4¢¢-H, 4¢¢¢¢-H, 5¢¢-H and 5¢¢¢¢-H), 7.40–7.42
(m, 2 H, 2¢¢¢¢-H and 6¢¢¢¢-H), 7.46–7.48 (m, 2 H, 2¢¢-H and 6¢¢-H).
13C NMR (75 MHz, CDCl3): d = 56.1 (CH3, OCH3), 71.0 (CH2, C-
2¢¢¢–OCH2Ph), 72.9 (CH2, C-1), 73.4 (CH2, C-3), 75.0 (CH2, C-2¢–
OCH2Ph), 106.6 (CH, C-4¢ or C-6¢), 107.3 (CH, C-4¢ or C-6¢),
114.7, 115.7, 121.5, 122.8 (CH, C-3¢¢¢, C-4¢¢¢, C-5¢¢¢ and C-6¢¢¢),
123.8 (CH, C-5¢), 127.3 (CH, C-2¢¢¢¢ and C-6¢¢¢¢), 127.8 (CH, C-4¢¢),
127.9 (CH, C-4¢¢¢¢), 128.1 (CH, C-3¢¢ and C-5¢¢ or C-3¢¢¢¢ and C-5¢¢¢¢),
128.4 (CH, C-2¢¢ and C-6¢¢), 128.5 (CH, C-3¢¢ and C-5¢¢ or C-3¢¢¢¢ and
C-5¢¢¢¢), 136.8 (C, C-1¢¢¢¢), 137.7 (C, C-1¢¢), 137.7 (C, C-2¢), 147.8
(C, C-1¢¢¢), 149.0 (C, C-2¢¢¢), 151.9 (C, C-1¢), 154.1 (C, C-3¢), 202.6
(C, C=O).
1H NMR (300 MHz, CDCl3): d = 3.13 (d, J = 4.6 Hz, 1 H, OH), 3.79
(s, 3 H, OCH3), 4.12–4.22 (m, 4 H, 2 × OCH2), 4.29–4.33 (m, 1 H,
CHOH), 4.98 (s, 2 H, C-2¢–OCH2Ph), 5.13 (s, 2 H, C-3¢¢¢–OCH2Ph),
6.54 (dd, J = 8.3, 1.2 Hz, 1 H, 4¢-H or 6¢-H), 6.56 (dd, J = 8.4, 1.1
Hz, 1 H, 4¢-H or 6¢-H), 6.92 (t, J = 8.4 Hz, 1 H, 5¢-H), 7.10 (s, 1 H,
1¢¢¢-H), 7.15 (s, 1 H, 4¢¢¢-H), 7.20–7.35 (m, 8 H, 3¢¢-H, 3¢¢¢¢-H, 4¢¢-H,
4¢¢¢¢-H, 5¢¢-H, 5¢¢¢¢-H, 6¢¢¢-H and 7¢¢¢-H), 7.41–7.45 (m, 4 H, 2¢¢-H,
2¢¢¢¢-H, 6¢¢-H and 6¢¢¢¢-H), 7.58–7.63 (m, 2 H, 5¢¢¢-H and 8¢¢¢-H).
13C NMR (75 MHz, CDCl3): d = 56.0 (CH3, OCH3), 68.5 (CH,
CHOH), 69.8 (CH2, C-3), 70.3 (CH2, C-1), 70.5 (CH2, C-3¢¢¢–
OCH2Ph), 75.1 (CH2, C-2¢–OCH2Ph), 106.0 (CH, C-4¢ or C-6¢),
107.4 (CH, C-4¢ or C-6¢), 108.8 (CH, C-4¢¢¢), 109.2 (CH, C-1¢¢¢),
123.8 (CH, C-5¢), 124.2 (CH, C-6¢¢¢ or C-7¢¢¢), 124.3 (CH, C-6¢¢¢ or
C-7¢¢¢), 126.3 (CH, C-5¢¢¢ or C-8¢¢¢), 126.4 (CH, C-5¢¢¢ or C-8¢¢¢),
127.2 (CH, C-2¢¢¢¢ and C-6¢¢¢¢), 127.7 (CH, C-4¢¢ or C-4¢¢¢¢), 127.8
(CH, C-4¢¢ or C-4¢¢¢¢), 128.0 (CH, C-2¢¢ and C-6¢¢), 128.1 (CH, C-3¢¢
and C-5¢¢ or C-3¢¢¢¢ and C-5¢¢¢¢), 128.5 (CH, C-3¢¢ and C-5¢¢ or C-3¢¢¢¢
and C-5¢¢¢¢), 129.2 (C, C-8¢¢¢a), 129.4 (C, C-4¢¢¢a), 136.7 (C, C-1¢¢¢¢),
137.7 (C, C-1¢¢), 137.8 (C, C-2¢), 148.7 (C, C-2¢¢¢), 148.8 (C, C-3¢¢¢),
152.6 (C, C-1¢), 153.8 (C, C-3¢).
MS (EI, 70 eV): m/z (%) = 484 (2.5, [M]+), 376 (1), 345 (2), 327 (3),
285 (1.5), 267 (2), 255 (1), 237 (6.5), 213 (1.5), 195 (3), 181 (4), 177
(3.5), 151 (3), 147 (5), 135 (4.5), 121 (2.5), 91 (100), 60 (6.5), 44
(3).
HRMS (EI): m/z [M]+ calcd for C30H28O6: 484.1886; found:
484.1877.
MS (EI, 70 eV): m/z (%) = 536 (12, [M]+), 518 (0.5), 446 (1), 428
(0.5), 396 (0.5), 340 (4) 306 (2), 286 (1), 250 (3.5), 229 (2.5), 199
(4), 171 (3), 160 (3.5), 139 (2.5), 131 (3), 115 (2.5), 91 (100), 65 (7),
39 (4).
8-Methoxy-3H,3¢H-2,2¢-spirobi(benzo[b][1,4]dioxine) (11)
Spiroketal 11 was prepared as described above for spiroketal 8,
from reaction of 10% Pd/C (25 mg, 0.23 mmol) with ketone 17 (54
mg, 0.11 mmol) in anhyd EtOAc (1 mL) at r.t. under H2 for 7 h, fol-
lowed by subsequent reaction of p-TsOH·H2O (27 mg, 0.14 mmol)
with hemiketal intermediate in anhyd CH2Cl2 (1 mL) at 50 °C for 4
h; yield: 23 mg (72%); colorless solid; mp 134.5–135.5 °C.
HRMS (EI): m/z [M]+ calcd for C34H32O6: 536.2199; found:
536.2203.
1-[2-(Benzyloxy)-3-methoxyphenoxy]-3-[3-(benzyloxy)naph-
thalen-2-yloxy]propan-2-one (18)
Ketone 18 was prepared as described above for ketone 16, from re-
action of TPAP (20 mg, 0.057 mmol) and NMO (47 mg, 0.403
mmol) with alcohol 35 (108 mg, 0.201 mmol) in anhyd CH2Cl2 (1.5
mL) containing activated 4Å MS (20 mg) at r.t. for 1.5 h; yield: 70
mg (65%); pale yellow oil that solidified as a cream-colored solid
upon standing; mp 101–102 °C.
IR (film): 3043, 2925, 2852, 1494, 1478, 1270, 1256, 1214, 1124,
1108, 1093 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.80 (s, 3 H, OCH3), 4.09 (d,
J = 11.3 Hz, 1 H, 3-HA), 4.16 (d, J = 11.3 Hz, 1 H, 3¢-HA), 4.24 (d,
J = 11.3 Hz, 1 H, 3-HB), 4.26 (d, J = 11.3 Hz, 1 H, 3¢-HB), 6.55 (dd,
J = 8.2, 1.2 Hz, 1 H, 5-H or 7-H), 6.63 (dd, J = 8.4, 1.4 Hz, 1 H, 5-
H or 7-H), 6.86 (t, J = 8.3 Hz, 1 H, 6-H), 6.87–6.99 (m, 4 H, 5¢-H,
6¢-H, 7¢-H and 8¢-H).
13C NMR (100 MHz, CDCl3): d = 56.3 (CH3, OCH3), 65.4 (CH2, C-
3), 65.5 (CH2, C-3¢), 91.4 (C, C-2), 105.6 (CH, C-5 or C-7), 109.7
(CH, C-5 or C-7), 117.2 (CH, C-5¢ or C-6¢ or C-7¢ or C-8¢), 117.7
(CH, C-5¢ or C-6¢ or C-7¢ or C-8¢), 121.4 (CH, C-6), 122.3 (CH, C-
5¢ or C-6¢ or C-7¢ or C-8¢), 122.4 (CH, C-5¢ or C-6¢ or C-7¢ or C-8¢),
130.7 (C, C-8a), 140.9 (C, C-8¢a), 142.1 (C, C-4¢a), 143.1 (C, C-4a),
149.2 (C, C-8).
IR (film): 3065, 3033, 2936, 1745, 1476, 1258, 1177, 1114 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.82 (s, 3 H, OCH3), 4.89 (s, 2 H,
C-2¢¢¢–OCH2), 4.90 (s, 2 H, C-1¢–OCH2), 5.05 (s, 2 H, C-2¢–
OCH2Ph), 5.20 (s, 2 H, C-3¢¢¢–OCH2Ph), 6.43 (dd, J = 8.4, 1.1 Hz,
1 H, 4¢-H or 6¢-H), 6.62 (dd, J = 8.4, 1.0 Hz, 1 H, 4¢-H or 6¢-H), 6.91
(t, J = 8.4 Hz, 1 H, 5¢-H), 7.02 (s, 1 H, 1¢¢¢-H), 7.20 (s, 1 H, 4¢¢¢-H),
7.22–7.37 (m, 8 H, 3¢¢-H, 3¢¢¢¢-H, 4¢¢-H, 4¢¢¢¢-H, 5¢¢-H, 5¢¢¢¢-H, 6¢¢¢-H
and 7¢¢¢-H), 7.46–7.49 (m, 4 H, 2¢¢-H, 2¢¢¢¢-H, 6¢¢-H and 6¢¢¢¢-H),
7.58–7.66 (m, 2 H, 5¢¢¢-H and 8¢¢¢-H).
13C NMR (75 MHz, CDCl3): d = 56.1 (CH3, OCH3), 70.6 (CH2, C-
3¢¢¢–OCH2Ph), 72.6 (CH2, OCH2), 72.9 (CH2, OCH2), 75.1 (CH2, C-
2¢–OCH2Ph), 106.7 (CH, C-4¢ or C-6¢), 107.3 (CH, C-4¢ or C-6¢),
109.1 (CH, C-4¢¢¢), 109.5 (CH, C-1¢¢¢), 123.8 (CH, C-5¢), 124.4 (CH,
C-6¢¢¢ or C-7¢¢¢), 124.7 (CH, C-6¢¢¢ or C-7¢¢¢), 126.3 (CH, C-5¢¢¢),
Synthesis 2007, No. 9, 1392–1402 © Thieme Stuttgart · New York