Anand et al.
(d, J ) 3 Hz, 1H), 12.41 (d, J ) 3 Hz, 1H), 12.14 (d, J ) 6 Hz,
1H), 11.67 (d, J ) 6 Hz, 1H), 11.22 (d, J ) 6 Hz, 1H), 11.08 (d,
J ) 6 Hz, 1H), 11.05 (d, J ) 6 Hz, 1H), 9.83 (d, J ) 6 Hz, 1H),
9.78 (s, 2H), 9.64 (d, J ) 6 Hz, 1H), 7.68 (s, 2H), 7.61 (s, 2H),
7.6 (s, 2H), 7.59 (s, 2H), 2.82 (s, 3H). 2.8 (s, 3H), 2.78 (s, 3H),
2.77 (s, 3H), 2.19 (s, 6H), 1.95 (s, 6H), 1.93 (s, 6H), 1.9 (s, 6H),
-0.75 (d, J ) 6 Hz, 1H), -4.92 (d, J ) 6 Hz, 1H), -6.27 (br s,
NH), -6.34 (br s, NH). 77Se NMR (CDCl3, 298 K): δ 557 (s)
and 537 (s). UV-vis (CH2Cl2) [λmax (nm) (104ꢀ)]: 571 (16.7),
677 (1.7), 731 (1.8), 797 (4.6); (CH2Cl2/TFA) 610 (30.4), 637
(14.8), 853 (0.9), 901 (1.5), 965 (6.1). FAB MS: m/z 1158. Anal.
Calcd for C68H58N2S3Se2: C, 70.57; H, 5.05; N, 2.42. Found:
C, 70.54; H, 5.02; N, 2.43.
3 Hz, 1H), 10.75 (s, 1H), 10.04 (d, J ) 3 Hz, 1H), 9.99 (s, 2H),
9.93 (m, 1H), 7.63 (s, 4H), 7.6 (s, 4H), 4.82 (s, 3H), 2.85-2.8
(m, 12H), 2.14 (s, 12H), 1.93 (s, 12H), -5.39 (s, 1H), -6.96 (s,
NH), -7.01 (s, NH), -7.69 (s, 3H). UV-vis (CH2
Cl2) [λmax (nm)
(104ꢀ)]: 567 (46.6), 595 (33.6), 820 (16.8), 669 (5), 993 (1.9);
(CH2Cl2/TFA) 598 (58.8), 636 (32.3), 980 (18.5). FAB MS: m/z
1092 [M+] (100%). Anal. Calcd for C70H62N2S5: C, 77.02; H,
5.72; N, 2.57. Found: C, 76.99; H, 5.76; N, 2.55.
Gen er a l P r oced u r e for Cou p lin g Rea ction s. Procedure
and experimental details for 13a 30 and 14a -d 11 have already
been reported elsewhere.
5,10,15,24-Tetr a p h en yl-29,34-d ith ia -31-selen a h exa p h y-
r in (13b). A mixture of tetrapyrrane 12a (0.32 g; 0.68 mmol)
and 5,10-diphenyl-16-selenatripyrrane (11b) (0.3 g; 0.68 mmol)
in dry dichloromethane (200 mL) was stirred under nitrogen
atmosphere for 15 min at room temperature. Trifluoroacetic
acid (0.15 g, 1.36 mmol) was added to the above mixture. The
solution immediately turned dark green, and stirring was
continued for another 1 h. The resulting solution was exposed
to air, chloranil (0.17 g; 0.68 mmol) was added, and the mixture
was heated to reflux in a preheated oil bath at 45 °C for 1 h.
After removal of the solvent the crude product was purified
by column chromatography using basic alumina grade III. The
first fraction was a pink band which moved in 1:1dichlo-
romethane/petroleum ether and gave a dark green solid, which
was identified as 12b (0.12 g, 20%). The second purple band
eluted with 49:1 dichloromethane/ethyl acetate gave a green
solid, which was identified as 13b (0.02 g; 4%). These com-
pounds were recrystallized from a 1:1 dichloromethane/n-
hexane mixture. 1H NMR (400 MHz, CDCl3/TFA, 298 K): δ
11.43 (d, 1H, J ) 4.4 Hz), 11.21 (d, 1H, J ) 4.8 Hz), 10.65 (d,
1H, J ) 4.4 Hz), 10.53 (d, 1H, J ) 4.8 Hz), 10.36-10.34 (m,
2H), 9.81 (d, 1H, J ) 4.4 Hz), 9.55 (d, 1H, J ) 4.5 Hz), 9.52 (d,
1H, J ) 4.4 Hz), 9.34 (d, 1H, J ) 5.2 Hz), 8.91-8.87 (m, 8H),
8.75-8.7 (m, 12H), -0.64 (s, 1H), -1.59 (s, 1H), -3.01 (d, 1H,
J ) 5.1 Hz), -3.21 (d, 1H, J ) 3.9 Hz), -4.58 (s, 1H). UV-vis
(CH2Cl2) [λmax (nm) (104ꢀ)]: 530 (10.72), 652 (1.09), 708 (0.86),
807 (0.41), 909 (0.35); (CH2Cl2/TFA) 564 (16.69), 748 (0.82),
838 (1.64), 911 (1.77). FAB mass [m/z (%)]: 844 (50) [M + 2]+.
Anal. Calcd for C52H33N3S2Se: C, 74.10; H, 3.95; N, 4.99.
Found: C, 74.12; H, 3.93; N,4.95.
5,10,19,24-Tet r a m esit yl-33,34,35-t r it h ia -37,38-d ioxa -
h ep ta p h yr in (10b). 8 (0.1 g, 0.15 mmol) and 9b (0.08 g, 0.15
mmol) in CH2Cl2 (100 mL) were subjected to conditions similar
to those mentioned above with TFA (0.01 mL, 0.15 mmol) and
chloranil (0.04 g, 0.15 mmol). Purification by column chroma-
tography on basic alumina gave a purple colored band with
95:5 CH2Cl2/EtOAc identified as 10b, which yielded a brownish
metallic solid on evaporation of solvent. Yield: 0.025 g, 15%.
10b decomposes above 280 °C. 1H NMR (300 MHz, CDCl3,
298K): δ 10.67 (d, J ) 6 Hz, 1H), 10.46 (d, J ) 6 Hz, 1H),
10.17 (d, J ) 6 Hz, 1H), 9.85 (d, J ) 3hz, 1H), 9.49 (d, J ) 3
Hz, 1H), 9.37 (d, J ) 3 Hz, 1H), 8.78 (d, J ) 6 Hz, 1H), 8.31 (s,
2H), 8.26 (d, J ) 3 Hz, 1H), 8.14 (d, J ) 3 Hz, 1H), 7.45 (s,
2H), 7.3 (s, 3H), 7.26 (s, 3H), 2.67 (s, 6H), 2.63 (s, 6H), 2.6 (s,
12H), 2.58 (s, 12H), -0.64 (d, J ) 3 Hz, 1H), -1.41 (d, J ) 3
1
Hz, 1H). H NMR (300 MHz, CDCl3/TFA, 258 K): δ 12.33 (d,
J ) 3 Hz, 1H), 12.07 (d, J ) 3 Hz, 1H), 11.56 (d, J ) 6 Hz,
1H), 11.37 (d, J ) 3 Hz, 1H), 10.96 (d, J ) 3 Hz, 1H), 10.75 (d,
J ) 6 Hz, 1H), 10.15 (d, J ) 6 Hz, 1H), 9.79 (d, J ) 6 Hz, 1H),
9.58 (s, 2H), 9.43 (d, J ) 3 Hz, 1H), 7.7 (s, 2H), 7.57 (s,
2H), 7.56 (s, 2H), 7.51 (s, 2H), 2.85 (s, 3H), 2.79 (s, 3H), 2.75
(s, 3H), 2.73 (s, 3H), 2.26 (s, 6H), 1.99 (s, 6H), 1.86 (s, 6H),
1.85 (s, 6H), -4.68 (s, 1H), -4.71 (s, 1H), -4.87 (br s, NH),
-5.77 (br s, NH). UV-vis (CH2Cl2) [λmax (nm) (104ꢀ)]: 555
(76.4), 581 (51.2), 637 (0.96), 660 (0.82), 805 (25.5); (CH2Cl2/
TFA) 586 (78.5), 635 (36.5), 656 (0.96), 909 (1.4), 946 (24.1),
1015 (1.4). FAB MS: m/z 1032 [M+] (100%). Anal. Calcd for
C
68H58N2S3O2: C, 79.19; H, 5.67:, N, 2.72. Found: C, 79.23;
H, 5.62; N, 2.69.
5,10,15,24-Tetr a p h en yl-29,34-d iselen a -31-th ia h exa p h y-
r in (13c). Tetrapyrrane 12b (0.59 g; 1.04 mmol) and 5,10-
diphenyl-16-thiatripyrrane (11a ) (0.41 g; 1.04 mmol), trifluo-
roacetic acid (0.24 g, 2.1 mmol), and chloranil (0.51 g; 2.1
mmol) in dry dichloromethane under reaction conditions
similar to those mentioned above gave 14c (0.18 g; 19%) and
5,10,19,24-Tetr a m esityl-13,16-d im eth yl-33,34,35,37,38-
p en ta th ia h ep ta p h yr in (10c). 8 (0.2 g, 0.31 mmol) and 9c
(0.15 g, 0.31 mmol) were subjected to conditions similar to
those mentioned above with TFA (0.025 mL, 0.31 mmol) and
chloranil (0.075 g, 0.31 mmol). Purification by column chro-
matography on basic alumina gave a purple colored band with
3:2 CH2Cl2/petroleum ether identified as 10c, which yielded a
brownish metallic solid on evaporation of solvent. Yield: 0.07
g, 20%. 10c decomposes above 250 °C. Data for conformer I:
1H NMR (400 MHz, CDCl3, 298 K) δ 10.47 (d, J ) 4 Hz, 1H),
10.4 (d, J ) 4 Hz, 1H), 10.37 (d, J ) 4 Hz, 1H), 10.22 (d, J )
4 Hz, 1H), 9.7 (s, 1H), 9.38 (d, J ) 4 Hz, 1H), 9.24 (d, J ) 4
Hz, 1H), 8.25 (m, 2H), 8.11 (d, J ) 4 Hz, 1H), 8.02 (d, J ) 4
Hz, 1H), 7.34-7.3 (m, 8H), 2.7 (s, 3H), 2.64-2.61 (m, 12H),
2.15 (m, 24H), -0.15 (s, 1H), -3.86 (s, 3H); 1H NMR (300 MHz,
CDCl3/TFA, 228 K) δ 12.7 (d, J ) 6 Hz, 1H), 12.54 (d, J ) 6
Hz, 1H), 12.43 (d, J ) 3 Hz, 1H), 12.16 (d, J ) 6 Hz, 1H), 1.26
(d, J ) 6 Hz, 1H), 11.05 (d, J ) 3 Hz, 1H), 9.93 (m, 1H), 9.87
(d, J ) 3 Hz, 1H), 9.68 (d, J ) 6 Hz, 1H), 9.58 (d, J ) 3 Hz,
1H). 7.68 (s, 4H), 7.56 (s, 4H), 3.14 (s, 3H), 2.8-2.75 (m, 12H),
2.14-2.0 (m, 24H), -4.67 (s, 1H), -5.51 (s, NH), -7.06 (s, NH),
-7.13 (s, 3H). Data for conformer II: 1H NMR (400 MHz,
CDCl3, 298 K) δ 10.7 (d, J ) 8 Hz, 1H), 10.65 (d, J ) 8 Hz,
1H). 10.61 (d, J ) 8 Hz, 1H), 10.46 (d, J ) 4 Hz, 1H), 9.58 (d,
J ) 8 Hz, 1H), 9.53 (d, J ) 4 Hz, 1H), 9.24 (s, 1H), 8.4 (m,
2H), 8.25 (m, 2H), 7.34-7.3 (m, 8H), 4.02 (s, 3H), 2.64 (s, 6H),
2.61 (s, 6H), 2.04 (s, 12H), 2.0 (s, 12H), -0.64 (s, 1H), -4.34
1
13c (0.03 g; 3%). H NMR (400 MHz, CDCl3,, 298K): δ 11.13
(s, 2H), 10.37 (d,1H, J ) 4.8 Hz), 10.33 (d, 1H, J ) 4.8 Hz),
9.67 (d, 1H, J ) 5.2 Hz), 9.58 (d, 1H, J ) 4 Hz), 9.03 (d, 1H,
J ) 4 Hz), 8.93 (d, 1H, J ) 4 Hz), 8.76 (d, 1H, J ) 4.3 Hz), 8.6
(d, 1H, J ) 4.3 Hz), 8.47 (d, 2H, J ) 7.3 Hz), 8.38-8.32 (m,
6H), 7.88-7.7 (m, 12H), -1.83 (s, 1H), -2.72 (s, 1H). 1H NMR
(400 MHz, CDCl3, TFA, 298 K): δ 11.5 (d, 1H, 4.8 Hz), 11.2
(d, 1H, J ) 5.2 Hz), 10.95 (d, 1H, J ) 4.8 Hz), 10.81 (d, 1H, J
) 5.2 Hz), 10.44 (d, 1H, J ) 4.4 Hz), 10.4 (d, 1H, J ) 4.8 Hz),
9.82 (d, 1H, J ) 4.4 Hz), 9.72 (d, 1H, J ) 4.4 Hz), 9.58 (d, 1H,
J ) 4.8 Hz), 9.51 (d, 1H, J ) 5.2 Hz), 8.97-8.93 (m, 4H), 8.85
(d, 2H, J ) 7.6 Hz), 8.75 (d, 2H, J ) 6.4 Hz), 8.24-7.97 (m,
12H), -1.27 (s, 1H), -2.11 (br.s,1H), -3.49 (d, 1H, J ) 5.2
Hz), -3.57 (d, 1H, J ) 4 Hz), -5.49 (s, 1H). UV-vis (CH2Cl2)
[λmax (nm) (104ꢀ)]: 549 (8.96), 680 (0.51), 743 (0.3), 861 (0.04),
987 (0.23); (CH2Cl2/TFA) 579 (10.5), 659 (0.02), 721 (0.19), 774
(0.23), 868 (0.81), 937 (0.74). FAB mass: [m/z (%)]: 890 (45)
[M + 1]+. Anal. Calcd for C52H33N3SSe2: C, 70.19; H, 3.14; N,
4.72. Found: C, 70.21; H, 3.09; N, 4.75.
5,10,15,24-Tet r a p h en yl-29,31,34-t r iselen a h exa p h yr in
(13d ). Tetrapyrrane 12b (0.47 g; 0.99 mmol) and 5,10-
1
(s, 3H); H NMR (300 MHz, CDCl3/TFA, 228 K) δ 12.89 (d, J
(30) Pushpan, S. K.; Anand, V. G.; Venkatraman, S.; Srinivasan,
A.; Gupta, A. K.; Chandrashekar, T. K. Tetrahedron Lett. 2001, 42,
3391.
) 3 Hz, 1H), 12.78 (d, J ) 6 Hz, 1H), 12.64 (d, J ) 3 Hz, 1H),
12.37 (d, J ) 3 Hz, 1H), 11.4 (d, J ) 6 Hz, 1H), 11.27 (d, J )
6318 J . Org. Chem., Vol. 67, No. 18, 2002