P. Rajakumar, S. Selvam / Tetrahedron 63 (2007) 8891–8901
8897
Found: C, 82.55; H. 5.49] dH (500 MHz, CDCl3) 7.99 (d, 2H,
J 9.2 Hz, Ar), 7.87 (d, 2H, J 8.4 Hz, Ar), 7.52 (d, 2H,
J 9.2 Hz, Ar), 7.18–7.35 (m, 14H, Ar), 5.66–5.70 (m,
2H, OH), 4.95 (d, 2H, J 12.2 Hz, OCH2), 4.73 (d, 2H,
J 12.2 Hz, OCH2), 4.40 (s, 2H, OCH); dC (125 MHz,
CDCl3) 153.9, 139.2, 136.6, 134.6, 129.4, 129.1, 128.5,
128.1, 127.7, 126.5, 125.7, 123.8, 121.2, 116.4, 82.1, 70.5;
m/z 524 (M+).
7.07–7.18 (m, 6H, Ar), 6.71 (d, 4H, J 7.8 Hz, Ar), 6.58 (d,
4H, J 7.8 Hz, Ar), 6.50 (s, 4H, Ar and CH]CH), 5.06 (d,
2H, J 16.2 Hz, OCH2), 4.88 (d, 2H, J 16.2 Hz, OCH2),
4.85 (s, 4H, NCH2); dC (125 MHz, CDCl3) 152.5, 139.9,
136.5, 133.6, 129.8, 129.3, 128.4, 126.9, 125.2, 125.4,
124.5, 123.8, 122.8, 122.5, 120.3, 116.8, 115.6, 109.2,
67.5, 49.4; m/z (FABMS) 748 (M+).
6.2.9. trans-1020-Di-[(S)-(L)-2,3:4,5-di(1,2-naphtho)-
1,6,13,19-tetraoxa-quadricyclo[21.29,10.226,27.229,30.128]-
triaconta-2,4,8,10,14(28),15,17,21,23,26,29-undece]-
ethene (5). White solid; yield 25%; hexane/CHCl3 (7:3);
[a]2D5 ꢁ272.5 (c 0.1, CHCl3); mp 155 ꢀC; [Elemental anal.
calcd for C86H64O8: C, 84.29; H, 5.26. Found: C, 84.42;
H, 5.34] dH (500 MHz, CDCl3) 7.94 (t, 4H, J 9.1 Hz, Ar),
7.87–7.89 (m, 4H, Ar), 7.54 (d, 2H, J 8.4 Hz, Ar), 7.32–
7.40 (m, 10H, Ar), 7.23–7.25 (m, 8H, Ar), 6.93 (d, 4H,
J 7.7 Hz, Ar), 6.89 (d, 4H, J 7.7 Hz, Ar), 6.84 (d, 4H, J
7.7 Hz, Ar), 6.78 (d, 4H, J 8.4 Hz, Ar), 6.58 (d, 2H,
J 6.9 Hz, Ar), 6.26 (s, 2H, Ar), 4.98–5.20 (m, 16H,
OCH2); dC (125 MHz, CDCl3) 158.6, 156.2, 153.8, 153.7,
137.0, 136.4, 134.3, 129.4, 128.1, 126.9, 126.7, 126.5,
125.4, 123.7, 121.3, 120.9, 120.4, 120.2, 115.4, 115.2,
110.6, 100.2, 70.1, 69.9, 69.8, 69.7; m/z (FABMS) 1225 (M+).
6.2.5. (S)-(L)-2,3:4,5-Di(1,2-naphtho)-1,6-dioxa-tricy-
clo[16.39–11.121.122]docosa-2,4,8,10,12(22),15(21),16,18-
octaene-13,14-diol (2b). Pale green solid; yield: 7%;
hexane/CHCl3 (3:7); mp 110 ꢀC; [a]D25 ꢁ56.2 (c 0.1,
CHCl3); [Elemental anal. calcd for C36H28O4: C, 82.42; H,
5.38. Found: C, 82.53; H. 5.46] dH (500 MHz, CDCl3)
7.81–7.84 (m, 2H, Ar), 7.76–7.78 (m, 2H, Ar), 7.47–7.50
(m, 2H, Ar), 7.22–7.25 (m, 2H, Ar), 7.06–7.12 (m, 6H,
Ar), 7.00–7.06 (m, 4H, Ar), 6.54–6.58 (m, 2H, Ar), 5.21–
5.24 (m, 2H, OH), 4.50–4.62 (m, 4H, OCH2), 4.38–4.52
(m, 2H, CH); dC (125 MHz, CDCl3) 153.6, 139.4, 136.5,
134.6, 129.2, 129.0, 128.3, 127.8, 127.4, 126.0, 125.7,
123.5, 121.0, 116.3, 82.0, 70.1; m/z 524 (M+).
6.2.6. (S)-(L)-2,3:4,5-Di(1,2-naphtho)-1,6-dioxa-tri-
cyclo[18.49–12.08,13.016,21]docosa-2,4,8,10,12,16,18,20-oc-
taene-14,15-diol (2c). Pale green solid; yield: 8%; hexane/
CHCl3 (3:7); mp 150–152 ꢀC; [a]D25 ꢁ35.4 (c 0.1, CHCl3);
[Elemental anal. calcd for C36H28O4: C, 82.42; H, 5.38.
Found: C, 82.33; H. 5.30] dH (500 MHz, CDCl3) 7.85–
7.90 (m, 2H, Ar), 7.78–7.80 (m, 2H, Ar), 7.48–7.52 (m,
2H, Ar), 7.29–7.31 (m, 4H, Ar), 7.12–7.25 (m, 4H, Ar),
7.02–7.08 (m, 4H, Ar), 6.53–6.58 (m, 2H, Ar), 5.29–5.32
(m, 2H, OH), 4.66–4.85 (m, 4H, OCH2), 4.39–4.54 (m,
2H, CH); dC (125 MHz, CDCl3) 153.5, 139.4, 136.6,
134.8, 129.4, 127.9, 127.7, 127.4, 126.0, 123.8, 125.6,
120.9, 116.5, 82.9, 69.7; m/z 524 (M+).
6.3. General procedure for Wittig reaction
To the stirred suspension of NaH (1.65 mmol) in THF
(40 mL) at 0 ꢀC under nitrogen atmosphere, was added bis-
phosphonium salt (0.17 mmol) followed by aldehyde
(0.35 mmol) in THF (30 mL). The reaction mixture was
allowed to reflux for 12 h. Then the reaction mixture was
quenched by using saturated NH4Cl solution. The reaction
mixture was then dissolved in water and extracted with
CHCl3 (2ꢂ100 mL), washed with water (2ꢂ200 mL), brine
(100 mL), and dried over Na2SO4. The solvent was evapo-
rated under vacuum to obtain the crude product, which
was purified by column chromatography using hexane/chlo-
roform (2:3) as a eluant.
6.2.7. (S)-(L)-2,3:4,5-Di(1,2-naphtho)-1,6,13,24-tetraoxa-
pentocyclo[26.29,10.231,32.233,34.235,36.237,38]octatriconta-
2,4,8,10,14,16,18,20,22,26,28,31,33,35,37-pentadecaene
(3). White solid; yield 40%; hexane/CHCl3 (1:1); mp 118–
120 ꢀC; [a]D25 ꢁ97.6 (c 0.1, CHCl3); [Elemental anal. calcd
for C50H38O4: C, 85.44; H, 5.45. Found: C, 85.32; H, 5.56]
dH (500 MHz, CDCl3) 7.92–7.95 (m, 2H, Ar), 7.87 (d, 2H,
J 8.4 Hz, Ar), 7.39–7.42 (m, 2H, Ar), 7.34 (t, 2H, J 6.9 Hz,
Ar), 7.21–7.25 (m, 4H, Ar), 7.15 (d, 2H, J 8.4 Hz, Ar),
7.06–7.09 (m, 4H, Ar), 6.99–7.01 (m, 4H, Ar), 6.64–6.68
(m, 4H, Ar), 6.59 (d, 2H, J 9.2 Hz, Ar), 6.42 (s, 2H,
CH]CH), 4.96–5.12 (m, 8H, OCH2); dC (125 MHz,
CDCl3) 157.4, 156.6, 154.3, 137.2, 137.0, 134.3, 130.4,
129.9, 129.6, 128.8, 128.1, 127.0, 126.9, 126.8, 126.5,
125.6, 123.9, 115.4, 115.1, 71.2, 70.1; m/z (FABMS) 702
(M+).
6.3.1. 1040-Di-[(S)-(L)-2,3:4,5-di(1,2-naphtho)-1,6,13,19-
tetraoxa-quadricyclo[21.29,10.226,27.229,30.128]-15-cis-eth-
enyl-triaconta-2,4,8,10,14(28),15,17,21,23,26,29-
undece]benzene (6a). Light green solid; yield: 8%; hexane/
CHCl3 (7:3); mp 189 ꢀC; [a]D25 ꢁ390.3 (c 0.1, CHCl3); [Ele-
mental anal. calcd for C94H70O8: C, 85.04; H, 5.31. Found:
C, 84.91; H, 5.38] dH (500 MHz, CDCl3) 7.90–7.95 (m, 8H,
Ar), 7.38–7.51 (m, 6H, Ar), 7.30–7.37 (m, 6H, Ar), 7.20–
7.25 (m, 8H, Ar), 7.13–7.18 (m, 4H, Ar), 7.00–7.08
(m, 2H, Ar), 6.88–6.93 (m, 8H, Ar), 6.75–6.83 (m, 8H,
Ar), 6.51–6.62 (m, 2H, Ar), 6.25 (s, 2H, Ar), 5.11–5.20
(m, 6H, OCH2), 4.98–5.05 (m, 10H, OCH2); dC (125 MHz,
CDCl3) 163.5, 159.1, 156.6, 153.8, 153.6, 136.8, 136.4,
136.3, 134.3, 129.4, 128.1, 127.1, 127.0, 126.9, 126.8,
126.6, 125.4, 125.2, 123.9, 123.6, 122.9, 115.3, 115.2,
110.5, 100.2, 70.2, 69.9, 69.8, 69.5; m/z (FABMS) 1328
(M+).
6.2.8. (S)-(L)-2,3:4,5-Di(1,2-naphtho)-1,6-dioxa-13,22-di-
aza-14,15,20,21-bis(1,2-benzo)pentocyclo[24.29,10.229,30
.
2
33,34.131.132]tetratriconta-2,4,8,10,16(32),17,19(31),24,
26,29,33-undecaene (4). White solid; yield: 15%; hexane/
CHCl3 (1:1); mp 155 ꢀC; [a]D25 ꢁ98.1 (c 0.1, CHCl3); [Ele-
mental anal. calcd for C54N40N2O2: C, 86.60; H, 5.38; N,
3.74. Found: C, 86.73; H, 5.46; N, 3.91] dH (500 MHz,
CDCl3) 7.83 (d, 4H, J 9.3 Hz, Ar), 7.78 (d, 4H, J 7.8 Hz,
Ar), 7.49 (d, 4H, J 7.8 Hz, Ar), 7.26–7.28 (m, 2H, Ar),
6.3.2. 1040-Di-[(S)-(L)-2,3:4,5-di(1,2-naphtho)-1,6,13,19-
tetraoxa-quadricyclo[21.29,10.226,27.229,30.128]-15-cis-eth-
enyl-triaconta-2,4,8,10,14(28),15,17,21,23,26,29-unde-
ce]benzene (6b). Light green solid; yield 75%; hexane/
CHCl3 (7:3); mp 246 ꢀC; [a]D25 ꢁ411.9 (c 0.1, CHCl3);