M. Takahashi et al. / Tetrahedron 62 (2006) 3065–3074
3073
(0.23 g, 91%) as a pale yellow powder: mp 178–180 8C; IR
(KBr) 1589 cmK1 (C]C); MS (FABC) m/z 622 (MC),
623 (MHC); H NMR (CDCl3) d 0.92 (t, JZ6.9 Hz, 3H,
silica-gel column chromatography (80% chloroform, 20%
hexane) and recrystallization from chloroform–hexane
solution gave 3L (0.088 g, 69%) as a pale yellow powder:
mp 141–142 8C; UV (CHCl3) 357 nm (3 23,400), 375 nm (3
37,400), 396 nm (3 37,000); IR (KBr) 1589 cmK1 (C]C),
1718 cmK1 (C]O); MS (ESI, positive) m/z 1471.5
1
(CH2)5CH3), 1.32–1.44 (m, 4H, (CH2)3(CH2)2CH3), 1.58–
1.66 (m, 2H, (CH2)2CH2(CH2)2CH3), 1.77–1.85 (m, 2H,
CH2CH2(CH2)3CH3), 3.64 (t, JZ8.1 Hz, 2H, CH2(CH2)4-
CH3), 5.64 (s, 2H, CH2Cl), 5.95 (s, 4H, CH2), 6.84–6.98 (m,
2H, ArH), 7.39 (t, JZ8.3 Hz, 1H, ArH), 7.50–7.67 (m, 8H,
ArH), 8.31–8.40 (m, 8H, ArH); 13C NMR (CDCl3) d 14.1
(CH3), 22.7 (CH2), 28.5 (CH2), 30.1 (CH2), 31.5 (CH2), 31.8
(CH2), 39.0 (CH2), 62.7 (CH2), 63.0 (CH2), 102.0 (CH),
107.6 (CH), 107.7 (CH), 124.2 (CH), 124.7 (CH), 125.0
(CH), 125.1 (CH), 125.2 (CH), 126.1 (CH), 126.4 (CH),
126.6 (CH), 129.4 (C), 129.8 (C), 130.0 (C), 130.3 (CH),
130.9 (C), 131.0 (C), 138.2 (C), 160.4 (C), 160.7 (C). Anal.
Calcd for C43H39ClO2: C, 82.87; H, 6.31; N, 0.00. Found: C,
82.56; H, 6.17; N, 0.08.
1
(MNaO2C); H NMR (CDCl3) d 0.92 (t, JZ6.6 Hz, 6H,
(CH2)5CH3), 1.26–1.44 (m, 8H, (CH2)3(CH2)2CH3), 1.51–
1.62 (m, 4H, (CH2)2CH2(CH2)2CH3), 1.73–1.87 (m, 4H,
CH2CH2(CH2)3CH3), 3.58–3.64 (m, 4H, CH2(CH2)4CH3),
5.39 (s, 2H, CH2OBz), 5.91 (s, 4H, CH2O), 5.93 (s, 4H,
CH2O), 5.95 (s, 4H, CH2O), 6.82–6.95 (m, 9H, ArH), 7.33–
7.42 (m, 5H, ArH), 7.49–7.55 (m, 16H, ArH), 8.08–8.11 (m,
2H, BzH), 8.26–8.36 (m, 16H, ArH); 13C NMR (CDCl3) d
14.1 (CH3), 22.7 (CH2), 28.5 (CH2), 30.1 (CH2), 31.4 (CH2),
31.8 (CH2), 62.9 (CH2), 63.0 (CH2), 66.5 (CH2), 101.4
(CH), 102.0 (CH), 107.3 (CH), 107.6 (CH), 107.8 (CH),
124.7 (CH), 125.0 (CH), 125.2 (CH), 126.0 (CH), 126.3
(CH), 129.3 (CH), 128.4 (C), 128.9 (C), 129.2 (C), 129.8
(C), 130.2 (C), 130.8 (CH), 130.9 (C), 138.1 (C), 160.5 (C),
160.6 (C), 166.4 (C). Anal. Calcd for C100H88O8: C, 84.72;
H, 6.26; N, 0.00. Found: C, 84.74; H, 6.28; N, 0.00.
4.1.14. Synthetic procedure for 3B. A solution containing
7B (0.15 g, 0.16 mmol), 5 (0.018 g, 0.074 mmol), potassium
carbonate (0.028 g, 0.20 mmol), and 18-crown-6 (0.039 g,
0.15 mmol) in DMF (5 mL) was heated at 55 8C with
stirring under argon atmosphere. After 4 h, the reaction
mixture was cooled to room temperature, and poured into
saturated ammonium chloride solution to precipitate the
product. The precipitate was collected by filtration,
intensively washed with water, and dried in a vacuum to
afford a pale yellow solid. Purification of the residue by
silica-gel column chromatography (80% chloroform, 20%
hexane) and recrystallization from chloroform–hexane
solution gave 3B (0.11 g, 75%) as a pale yellow powder:
mp 135–137 8C; UV (CHCl3) 358 nm (3 33,800), 378 nm (3
54,700), 398 nm (3 54,100); IR (KBr) 1591 cmK1 (C]C),
1720 cmK1 (C]O); MS (ESI, positive) m/z 2020.9 (MNaC
), 2036.9 (MNaOC), 2052.9 (MNaO2C), 2069.0
4.1.16. Synthetic procedure for 4B. A solution containing
7B (0.55 g, 0.61 mmol), 6 (0.043 g, 0.075 mmol), potassium
carbonate (0.094 g, 0.68 mmol), and 18-crown-6 (0.18 g,
0.68 mmol) in DMF (10 mL) was heated at 55 8C with
stirring under argon atmosphere. After 4 h, the reaction
mixture was cooled to room temperature, and poured into
saturated ammonium chloride solution to precipitate the
product. The precipitate was collected by filtration,
intensively washed with water, and dried in a vacuum to
afford a yellow solid. Purification of the residue by the
preparative HPLC (chloroform as eluent) gave 4B (0.25 g,
57%) as a yellow powder: mp 136–137 8C; UV (CHCl3)
359 nm (3 106,000), 378 nm (3 171,000), 399 nm
(3 167,000); IR (KBr) 1593 cmK1 (C]C), 1728 cmK1
(C]O); MS (CSI, negative) m/z 2954.5 (MCl22K), 5873.3
(MClK); 1H NMR (CDCl3) d 0.88 (t, JZ6.9 Hz, 36H,
(CH2)5CH3), 1.28–1.37 (m, 48H, (CH2)3(CH2)2CH3), 1.52–
1.62 (m, 24H, (CH2)2CH2(CH2)2CH3), 1.71–1.83 (m, 24H,
CH2CH2(CH2)3CH3), 3.53–3.60 (m, 24H, CH2(CH2)4CH3),
5.31 (s, 6H, CH2OBz), 5.62 (s, 12H, OCH2), 5.66 (s, 12H,
OCH2), 5.74 (s, 24H, OCH2), 6.55 (s, 12H, ArH), 6.61 (s,
6H, ArH), 6.72 (s, 3H, ArH), 6.80 (s, 6H, ArH), 7.37–7.56
(m, 72H, ArH), 8.14–8.35 (m, 72H, ArH), 8.95 (s, 3H,
BzH); 13C NMR (CDCl3) d 14.1 (CH3), 22.7 (CH2), 28.4
(CH2), 30.0 (CH2), 31.4 (CH2), 31.7 (CH2), 62.6 (CH2), 62.9
(CH2), 67.1 (CH2), 94.8 (CH), 95.1 (CH), 102.1 (CH), 107.8
(CH), 124.7 (CH), 125.0 (CH), 125.1 (CH), 126.0 (CH),
126.1 (CH), 128.7 (C), 128.9 (C), 129.3 (C), 130.6 (C),
130.9 (C), 134.9 (C), 138.0 (C), 138.1 (C), 160.5 (C), 161.2
(C), 161.3 (C), 164.6 (C). Anal. Calcd for C414H384O30: C,
85.15; H, 6.63; N, 0.00. Found: C, 84.95; H, 6.43; N, 0.00.
1
(MNaO3C); H NMR (CDCl3) d 0.88 (t, JZ7.1 Hz, 12H,
(CH2)5CH3), 1.25–1.37 (m, 16H, (CH2)3(CH2)2CH3), 1.48–
1.55 (m, 8H, (CH2)2CH2(CH2)2CH3), 1.66–1.79 (m, 8H,
CH2CH2(CH2)3CH3), 3.45–3.57 (m, 8H, CH2(CH2)4CH3),
5.28 (s, 2H, CH2OBz), 5.74 (s, 16H, CH2O), 6.60 (s, 4H,
ArH), 6.62 (s, 2H, ArH), 6.82 (s, 3H, ArH), 7.26–7.35 (m,
3H, ArH), 7.38–7.50 (m, 24H, ArH), 8.02–8.04 (m, 2H,
BzH), 8.15–8.27 (m, 24H, ArH); 13C NMR (CDCl3) d 14.1
(CH3), 22.7 (CH2), 28.4 (CH2), 30.0 (CH2), 31.4 (CH2), 31.7
(CH2), 62.7 (CH2), 62.9 (CH2), 66.4 (CH2), 94.8 (CH), 95.0
(CH), 101.2 (CH), 107.3 (CH), 124.7 (CH), 125.0 (CH),
125.1 (CH), 126.0 (CH), 126.2 (CH), 128.3 (CH), 128.8 (C),
129.0 (C), 129.3 (C), 129.7 (CH), 130.0 (C), 130.6 (C),
130.7 (C), 130.9 (C), 133.0 (CH), 138.0 (C), 138.8 (C),
160.6 (C), 161.2 (C), 161.3 (C), 166.3 (C). Anal. Calcd for
C142H132O10: C, 85.34; H, 6.66; N, 0.00. Found: C, 85.28;
H, 6.63; N, 0.00.
4.1.15. Synthetic procedure for 3L. A solution containing
7L (0.12 g, 0.19 mmol), 5 (0.022 g, 0.090 mmol), potassium
carbonate (0.034 g, 0.25 mmol), and 18-crown-6 (0.047 g,
0.18 mmol) in DMF (5 mL) was heated at 55 8C with
stirring under argon atmosphere. After 4 h, the reaction
mixture was cooled to room temperature, and poured into
saturated ammonium chloride solution to precipitate the
product. The precipitate was collected by filtration,
intensively washed with water, and dried in a vacuum to
afford a pale yellow solid. Purification of the residue by
4.1.17. Synthetic procedure for 4L. A solution containing
7L (0.50 g, 0.80 mmol), 6 (0.058 g, 0.10 mmol), potassium
carbonate (0.13 g, 0.91 mmol), and 18-crown-6 (0.24 g,
0.91 mmol) in DMF (10 mL) was heated at 55 8C with
stirring under argon atmosphere. After 4 h, the reaction
mixture was cooled to room temperature, and poured into
saturated ammonium chloride solution to precipitate the
product. The precipitate was collected by filtration,