=7.1 Hz), 2.76 (t, 4H, J =7.1 Hz), 4.12 (d, 2H, J =16.7 Hz), 4.29 (s, 2H), 4.62 (d, 2H, J =16.7 Hz), 6.79 (s,
2H), 7.00 (d, 2H, J =8.2, 1.6 Hz), 7.05 (d, 2H, J =8.2 Hz). MS (EI) (m/z) 308 [M]+. HRMS (EI) (m/z)
Calcd for C H N : 308.2000. Found 308.2012. Anal. Calcd for C H N : C, 73.99; H, 7.84; N,
19 24 4
19 24 4
18.17. Found: C, 74.09; H, 7.65; N, 18.26.
Macrocycle (5)
A solution of 3 (456 mg, 0.68 mmol) in CH Cl (20 mL) and a mix solution of 4b (210 mg, 0.68 mmol)
2 2
and TEA (0.95 ml, 6.8 mmol) in CH Cl (20 mL) were added dropwise over a period of 3 h to a stirred
2 2
solution of collidine (824 mg, 6.8 mmol) in CH Cl (250 mL) at 60℃ under N , and the stirring was
2 2
2
continued at the same temperature for 36 h. The reaction mixture was evaporated under reduced
pressure. The residue was purified by column chromatography on silica gel with CHCl :MeOH:25%
3
NH OH (100:7:1) as an eluent to give 290 mg (70% (meso:dl =1:1) ) of a colorless powder. mp 295℃
4
1
(meso -isomer) (decomp).
H NMR (meso-isomer) (CDCl ) δ: 2.52-2.58 (m, 4H), 3.18 (2H, d, J =15.7
3
Hz), 3.25 (d, 2H J =15.7 Hz), 3.31-3.37 (m, 4H), 4.04 (d, 2H, J =11.4 Hz), 4.10 (d, 2H, J =11.4 Hz), 4.30
(s, 2H), 4.32 (s, 2H), 4.68 (d, 4H, J =16.5 Hz), 5.42 (brs, 2H), 6.53 (s, 2H), 6.59 (s, 2H), 6.83 (d, 2H, J
=8.1 Hz), 6.90 (d, 2H, J =8.1 Hz), 7.04 (d, 2H, J =8.7 Hz), 7.07 (d, 2H, J =9.0 Hz). MS (EI) (m/z) 610
[M]+. HRMS (EI) (m/z) Calcd for C H N O : 610.3056. Found 610.3064. Anal. Calcd for
38 38 6 2
1
C H N O : C, 74.77; H, 6.27; N, 13.77. Found: C, 74.52; H, 6.30; N, 13.93. H NMR (dl-isomer)
38 38 6 2
(CDCl ) δ: 2.18-2.53 (m, 4H). 3.10 (d, 2H, J =15.8 Hz), 3.28 (d, 2H, J =15.8 Hz), 3.32-3.42 (m, 4H),
3
4.07 (d, 4H, J =16.5), 4.27 (s, 4H), 4.66 (d, 4H, J =16.5 Hz), 5.31 (t, 2H, J =5.6 Hz), 6.60-6.67 (m, 6H),
6.78 (dd, 2H, J =8.3 and 1.8 Hz), 6.98 (d, 2H, J =8.1 Hz), 7.04 (d, 2H, J =8.1 Hz). mp 240°C (dl -
isomer) (decomp). Anal. Calcd for C H N O : C, 74.77; H, 6.27; N, 13.77. Found: C, 74.50; H,
38 38 6 2
6.30; N, 13.95.
Macrocycle (meso-isomer) (6a)
A suspension of 5 (meso-isomer) (277 mg, 0.45 mmol) in THF (5 mL) was stirred at 0℃ under N
2
.
atmosphere. BH SMe (0.53 mL, 5.49 mmol) was added. The reaction mixture was stirred for 24 h
3
2
at 80℃, then was cooled to rt. 0.7 M hydrogen chloride-MeOH solution was added, and the reaction
mixture was refluxed for 0.5 h, and evaporated under reduced pressure. The residue was made basic to pH
11 with excess 25% NH OH. The mixture was extracted with CH Cl (100 mL x 3). The combined
2 2
4
organic phases were washed with brine and dried over Na SO . Removal of solvent under reduced
2
4
pressure afforded a colorless foam, which was purified by column chromatography on silica gel with
CHCl :MeOH:25% NH OH=100:10:1) as an eluent to give 254 mg (96%) of a white powder. An
3
4
analytical sample was obtained by recrystallizing this material from MeOH, colorless needles. mp
1
293℃ (decomp). H NMR (CDCl ) δ: 2.54-2.77 (m, 16H), 3.99 (d, 4H, J =16.6 Hz), 4.28 (s, 4H), 4.60
3
13
(d, 4H, J =16.6 Hz), 6.62 (d, 4H, J =1.5 Hz), 6.91 (dd, 4H, J =8.2, 1.5 Hz), 6.97 (d, 4H, J =8.2 Hz). C
NMR (CDCl ) δ: 34.7, 50.0, 58.9, 67.1, 124.8, 127.1, 127.7, 128.0, 136.0, 146.0. MS (EI) (m/z) 582
3
[M]+. HRMS (EI) (m/z) Calcd for C H N : 582.3471. Found 582.3442. Anal. Calcd for
38 42 6
C H N : C, 78.32; H, 7.26; N, 14.42. Found: C, 78.39; H, 7.33; N, 14.24.
38 42 6
Macrocycle (6b)
A mixture of 6a (meso-isomer) (58 mg, 0.1 mmol), methyl acrylate (52 mg, 0.6 mmol) and