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145.32, 143.25, 135.79, 134.71, 132.42, 132.12, 131.50–
130.22, 128.61, 127.53–126.63, 125.50, 125.21, 122.56,
121.85, 121.07; HRMS (FAB+): m/z Calc. for
(S)-2,20-binaphtol
phosphorochloridite
(5.3 g,
15.1 mmol) was dissolved in THF (20 ml) and added
dropwise. The cooling bath was removed and the solu-
tion was allowed to warm to room temperature, stirring
was continued for 1 h. The reaction mixture was filtered
and the solvent evaporated. A mixture of toluene/hex-
ane 1/3 (40 ml) was added to extract the product. After
filtration the solvent was removed in vacuo, giving g
(5.4 g, 13.2 mmol, 87%) as a white solid: 0H NMR
(300 MHz): d 8.54 (d, 1H, J = 2.4 Hz), 8.40 (d, 1H,
J = 4.2 Hz), 8.02 (d, 1H, J = 8.7 Hz), 7.95 (d, 1H,
J = 8.7 Hz), 7.92 (d, 2H, J = 8.7 Hz), 7.56-7.16 (m,
C64H40N4O3PZn
([MH+]):
1007.2130;
Obsd.:
1007.2136. Anal. Calc. for C64H39N4O3PZn: C, 76.23;
H, 3.90; N, 5.56. Found: C, 76.29; H, 4.14; N, 5.22%.
4.2.5. Synthesis of (S)(1,10-binaphthyl-2,20-diyl)
(5-(phenyl-3-yl)-10,15,20-tris(phenyl) zinc(II)
porphyrin) phosphite 5
This compound was prepared as described for 3,
using 5-(3-hydroxyphenyl)-10,15,20-tris(phenyl) zinc(II)
porphyrin and freshly prepared (S)-2,20-binaphtol
phosphorochloridite. Yield (39%) as a purple-red solid:
1H NMR (300 MHz): d 8.97–8.94 (m, 6H), 8.83–8.78
(m, 2H), 8.24-8.21 (m, 6H), 8.04–7.79 (m, 6H), 7.77 (s,
9H) 7.70–7.15 (m, 10H); 31P NMR (121.5 MHz): d
142.49; 13C-ATP (75.465 MHz): d 150.53 (C), 150.28
(C), 144.83 (C), 143.01 (C), 134.67 (CH), 132.39 (CH),
132.02 (CH), 131.49 (C), 131.05 (CH), 130.76 (CH),
130.23 (CH), 128.61 (CH), 127.83 (CH), 127.31 (CH),
127.26 (CH), 126.83 (CH), 126.83 (CH), 126.63 (CH),
125.50 (CH), 125.23 (CH), 121.99 (CH), 121.49 (C),
120.19 (CH); HRMS (FAB+): m/z Calc. for
C64H40O3PZn ([MH+]): 1007.2129; Obsd.: 1007.2109.
Anal. Calc. for C64H39N4O3Zn: C, 76.23; H, 3.90; N,
5.56. Found: C, 76.36; H, 4.08; N, 5.42%.
10H); 31P NMR (121.5 MHz):
d
143.05; 13C
(75.465 MHz): 148.88 (d, Jcp = 6.1 Hz), 147.52 (d,
Jcp = 4.8 Hz), 146.154 (d, Jcp = 1.4 Hz), 145.80 (s),
142.71 (d, Jcp = 7.3 Hz), 133.02 (s), 132.75 (s), 132.01
(s), 131.55 (s), 130.97 (s), 130.36 (s), 129.29 (s), 128.67
(d, Jcp = 4.8 Hz), 128.48 (s), 127.945 (s), 127.83 (s),
127.28 (s), 127.19 (s), 126.80 (s), 126.67 (s), 125.68 (s),
125.49 (s), 124.49 (s) 121.77 (s), 121.59 (s). HRMS
(FAB+): m/z Calc. for C25H17NO3P ([MH+]):
410.0946; Obsd.: 410.0952. Anal. Calc. for
C25H16NO3P: C, 73.35; H, 3.94; N, 3.42. Found: C,
73.20; H, 4.16; N, 3.25%.
4.2.8. Synthesis of (R)(1,10-binaphthyl-2,20-diyl)
(3-pyridyl) phosphite h
This compound was prepared as described for g,
using 3-hydroxypyridine and freshly prepared (R)-2,20-
binaphtol phosphorochloridite. Yield (78%) as a pur-
ple-red solid: 1H NMR (300 MHz): d 8.54 (d, 1H,
J = 2.4 Hz), 8.40 (d, 1H, J = 4.2 Hz), 8.02 (d, 1H,
J = 8.7 Hz), 7.95 (d, 1H, J = 8.7 Hz), 7.92 (d, 2H,
J = 8.7 Hz), 7.56–7.16 (m, 10H); 31P NMR
(121.5 MHz): d 143.05; 13C-ATP (75.465 MHz): 148.88
(d, Jcp = 6.1 Hz), 147.52 (d, Jcp = 4.8 Hz), 146.84 (d,
Jcp = 1,4 Hz), 145.80 (s), 142.71 (d, Jcp = 7.3 Hz),
133.02 (s), 132.75 (s), 132.01 (s), 131.55 (s), 130.97 (s),
130.36 (s), 129.29 (s), 128.67 (d, Jcp = 4.8 Hz), 128.48
(s), 127.945 (s), 127.83 (s), 127.28 (s), 127.19 (s),
126.80 (s), 126.67 (s), 125.68 (s), 125.49 (s), 124.49 (s)
121.77 (s), 121.59 (s). HRMS (FAB+): m/z Calc. for
C25H17NO3P ([MH+]): 410.0946; Obsd.: 410.0938. Anal.
Calc. for C25H16NO3P: C, 73.35; H, 3.94; N, 3.42.
Found: C, 73.64; H, 4.38; N, 3.05%.
4.2.6. Synthesis of (S)(3,30-bis(trimethylsilyl)-1,1-
binaphthyl-2,20-diyl)(5-(phenyl-2-yl)-10,15,20-tris
(phenyl) zinc(II) porphyrin) phosphite 6
This compound was prepared as described for 3,
using freshly prepared (S)-3,30-bis(trimethylsilyl)-2,20-
binaphtol phosphorochloridite. Yield (51%) as a pur-
ple-red solid: 1H NMR (300 MHz): d 9.06 (d, 2H),
8.96 (d, 2H, J = 5.4 Hz), 8.85 (d, 2H, J = 5.1 Hz), 8.83
(m, 2H), 8.66 (m, 1H), 8.49 (m, 3H), 8.23 (m, 2H),
8.12 (m, 2H), 8.02 (m, 1H), 7.94 (d, 2H, J = 5.4 Hz),
7.84–7.55 (m, 9H), 7.45 (m, 1H), 7.37 (m, 2H), 7.22–
7.11 (m, 4H), 6.63 (m, 1H), 8.94 (m, 1H), 5.06 (m,
1H), 4.50 (m, 1H), 0.51 (s, 9H), 0.03 (s, 9H); 31P
NMR (121.5 MHz): d 150.03; 13C-ATP (75.465 MHz):
d 150.7, 150.5, 150.4, 145.4, 135.7, 134.7, 132.4, 132.1,
131.5–130.2, 128.7, 127.6–126.5, 125.4, 125.1, 122.5,
121.9, 121.1, 0.35, 0.20; HRMS (FAB+): m/z Calc. for
C70H56N4O3PSi2Zn ([MH+]): 1151.2930; Obsd.:
1151.2920. Anal. Calc. for C70H55N4O3PSi2Zn: C,
72.92; H, 4.81; N, 4.86. Found: C, 72.96; H, 4.83; N,
4.71%.
4.2.9. Synthesis of (S)(3,30-bis(trimethylsilyl)-1,10-
binaphthyl-2,20-diyl)(3-pyridyl) phosphite i
This compound was prepared as described for g,
using freshly prepared (S)-3,30-bis(trimethylsilyl)-2,20-
binaphtol phosphorochloridite. Yield (66%) as a white
4.2.7. Synthesis of (S)(1,10-binaphthyl-2,20-diyl)
(3-pyridyl) phosphite g
1
solid: H NMR (300 MHz): d 8.30 (d, 1H, J = 2.7 Hz),
3-Hydroxypyridine (1.44 g, 15.1 mmol), azeotropi-
cally dried with toluene (3 · 5 ml), and triethylamine
(2.3 ml, 16 mmol) were dissolved in THF (40 ml) and
the solution was cooled to ꢀ40 ꢁC. Freshly prepared
8.27 (d, 1H, J = 5.1 Hz), 8.08 (d, 2H, J = 2.7 Hz), 7.92
(dd, 2H, J = 2.7, 8.1 Hz), 7.45–7.40 (m, 2H), 7.39–7.31
(m, 1H), 7.26–7.09 (m, 5H), 0.43 (s, 9H), 0.38 (s, 9H);
31P NMR (121.5 MHz): d 138.99; HRMS (FAB+):