16
Tetrahedron
CH(CH3)2); Diastereomer 2: 8.25-6.76 (m, Ar), 5.72 (1H,
orange solid which was filtered to give [(S)-diphenyl[1-(2-
methylquinazolin-4-yl)(2-naphthyl)]phosphine-[1,3-diphenyl-π-
allyl]palladium] tetrafluoroborate 10b, (0.059 g, 91%) as a
yellow solid, decomposed 184-187°C . Found: C, 62.8; H, 4.2; N,
3.5. C46H36N2PPdBF4 requires C, 65.7; H, 4.3; N, 3.3 %; 1H
NMR (500 MHz): δ (CDCl3) Diastereomer 1 and 2: 8.29-6.39
(m, Ar-H); Diastereomer 1: 7.1 (1H, allyl trans P), 6.7 (1H,
central allyl), 4.74 (d, 1H, J = 10.3 Hz, allyl trans N) and 2.82 (s,
3H, CH3); Diastereomer 2: 6.02 (t, 1H, J = 11.9 Hz, central allyl
H), 5.77 (m, 2H, allyl trans P and allyl trans N) and 3.29 (s, 3H,
CH3): Diastereomer 1: Diastereomer 2 = 53:47; 31P NMR
(101.3MHz): δ (CDCl3) 31.4 (53%), 28.8 (47%); νmax (KBr) 3051
(w) (Ar-H), 1612 (w) (conj C=C), 1571 (m) (conj C=C), 1559
(m) (conj C=C), 1437 (m) (P-Ph), 1084 (br) (B-F) and 752 (m)
sept., J = 7.0 Hz, CH(CH3)2), 4.94 (1H, app d, J = 11.1, 5.6 Hz,
H3'), 4.06 (1H, app d, J = 7.0 Hz, H2'), 3.88 (1H, m, H1'), 3.65
(1H, m, H5'), 3.24 (1H, d, H4'), 1.69 (6H, d, J = 6.4 Hz,
CH(CH3)2); 31P NMR (121 MHz): δ (CDCl3) : 32.5 and 32.6
ppm; m/z ES+ (CH3OH): 631 (M+, 100), 499 (64), 483 (64).
[(R)-Diphenyl[1-(2-tert-butyl-quinazolin-4-yl)(2-
naphthyl)]phosphine-[π-allyl]palladium] tetrafluoroborate 8f.
Di-µ-chloro-bis(π-allyl)dipalladium 9, (0.018 g, 0.048 mmol),
(R)-diphenyl[1-(2-tert-butyl-quinazolin-4-yl)(2-
naphthyl)]phosphine 7f, (0.048 g, 0.096 mmol) and sodium
tetrafluoroborate (0.021 g, 0.193 mmol) were placed in a Schlenk
tube under nitrogen. Dry degassed dichloromethane (2 mL) was
added via syringe to give a yellow suspension which was stirred
overnight. The reaction mixture was filtered and petroleum ether
was added to precipitate a fine yellow solid which was filtered
again to give [(R)-diphenyl [1-(2-tert-butyl-quinazolin-4-yl)(2-
naphthyl)]phosphine-[π-allyl]palladium] tetrafluoroborate 8f,
(0.061 g, 85%), m.p.220˚C, νmax (KBr) 3072, 2960, 2865, 1549,
(Ar-H) cm-1; [α]20 -405.6 (c 0.50,CHCl3); m/z (esi / pos in
CH3OH) cation 754 = M-BF4.
D
[(R)-Diphenyl[1-(2-phenylmethylquinazolin-4-yl)(2-
naphthyl)]phosphine-[1,3-diphenyl-π-allyl]palladium]
tetrafluoroborate
10c.
Di-µ-chloro-bis(1,3-diphenyl-π-
1458, 1382, and 1024 cm-1; H NMR (300 MHz): δ (CDCl3)
allyl)dipalladium 11 (0.015 g, 0.023 mmol), (R)-diphenyl[1-(2-
phenylmethylquinazolin-4-yl)(2-naphthyl)]phosphine 7c (0.024
g, 0.045 mmol) and sodium tetrafluoroborate (0.010 g, 0.090
mmol) were placed in a Schlenk tube under an atmosphere of
nitrogen. Dry, degassed dichloromethane (2 mL) was added via
syringe to give an orange suspension which was stirred overnight
(22 h) at room temperature under an atmosphere of nitrogen. The
solid was removed by filtration and diethyl ether was added to
precipitate an orange solid which was filtered to give [(R)-
diphenyl[1-(2-phenylmethylquinazolin-4-yl)(2-
1
Diastereomer 1: 7.99-7.19 ppm (m, Ar), 6.68 (d, Ar-H), 5.41
(1H, m, H3), 4.31 (1H, app t, J = 12.9, 7.1 Hz, H2), 4.11 (1H, d, J
= 6.9 Hz, H5), 2.75 (1H, d, J = 7.3 Hz, H4), 2.51 (1H, t, J = 10.3
Hz, H1), 1.19 (9H, s, C(CH3)3); Diastereomer 2: 7.99-7.19 (m,
Ar), 6.68 (d, Ar-H), 4.62 (1H, m, H3'), 3.76 (1H, m, H2'), 3.44
(1H, t, J = 10.1 Hz), 2.84 (1H, d, J = 5.8 Hz, H4'), 1.57 (9H, s,
C(CH3)3); 31P NMR (121 MHz): δ (CDCl3) = 23.2 and 23.4 ppm;
m/z ES+ (CH3OH): 643 (M-BF4, 54), 497 (100).
[(S)-Diphenyl[1-(quinazolin-4-yl)(2-naphthyl)]phosphine-
[1,3-diphenyl-π-allyl]palladium] tetrafluoroborate 10a.[20] Di-
µ-chloro-bis(1,3-diphenyl-π-allyl)dipalladium 11, (0.044 g, 0.065
naphthyl)]phosphine-[1,3-diphenyl-π-allyl]palladium]
tetrafluoroborate 10c (0.023 g, 55%), Tdecomp > 142°C; νmax (KBr)
3057 (w, Ar-H), 2960 (w, C-H), 2924 (w, C-H), 1616 (m, conj
C=C), 1560 (m, Ar-H), 1489 (m, Ar-H), 1436 (m, P-Ph), 1084 (s,
br, B-F) and 804 (w, Ar-H) cm-1; 31P NMR (121 MHz): δ
(CD2Cl2) 41.8 and 38.8 ppm; m/z (ESI / pos in CH3OH) cation:
830 = M-BF4.
mmol),
(S)-diphenyl[1-(2-phenylquinazolin-4-yl)(2-
naphthyl)]phosphine 7a, (0.057 g, 0.13 mmol) and sodium
tetrafluoroborate (0.029 g, 0.26 mmol) were placed in a Schlenk
tube under nitrogen. Dry degassed dichloromethane (3 mL) was
added via syringe to give an orange suspension which was stirred
for 16 h. The solid was removed by filtration, then diethyl ether
was added to precipitate a yellow solid which was filtered to give
[(S)-diphenyl[1-(quinazolin-4-yl)(2-naphthyl)]phosphine-[1,3-
diphenyl-π-allyl]palladium] tetrafluoroborate 10a, (0.098 g, 91%)
as a yellow solid, m.p. 228-230˚C; [α]20D -535 (c = 0.19, CHCl3);
νmax (KBr) 1577 (conj C=C), 1436 (P-Ph), 1084 (B-F) and 896
[(S)-Diphenyl[1-(2-isopropyl-quinazolin-4-yl)(2-
naphthyl)]phosphine-[1,3-diphenyl-π-allyl]palladium]
tetrafluoroborate
10d.
Di-µ-chloro-bis(1,3-diphenyl-π-
allyl)dipalladium 11, (0.014 g, 0.020 mmol), (S)-diphenyl[1-(2-
isopropyl-quinazolin-4-yl)(2-naphthyl)]phosphine 7d, (0.020 g,
0.041 mmol) and sodium tetrafluoroborate (9.1 mg, 0.082 mmol)
were placed in a Schlenk tube under nitrogen. Dry degassed
dichloromethane (2 mL) was added via syringe to give an orange
suspension, a white precipitate was seen to crash out of the
solution. The reaction mixture was heated for 5 h at 40°C and the
white precipitate was removed by filtration. Petroleum spirit was
subsequently added and [(S)-diphenyl[1-(2-isopropyl-quinazolin-
4-yl)(2-naphthyl)]phosphine-[1,3-diphenyl-π-allyl]palladium]
tetrafluoroborate 10d (0.026 g, 73%) was collected by filtration.
The yellow solid was dried under vacuum. m.p.231-233˚C; νmax
(KBr) 3056, 2963, 2923, 1613, 1559, 1503, 1435 and 1020 cm-1;
1H NMR (500 MHz): δ (CDCl3) Diastereomer 1: 8.64-6.52 (m,
Ar), 6.39 (1H, app t, J = 11.7 Hz, central allyl), 4.28 (1H, sept., J
= 6.5 Hz, CH(CH3)2), 3.92 (1H, d, J = 11.7 Hz, trans to
nitrogen), 3.46 (1H, dd, J = 12.4, 7.2 Hz, trans to phosphorus),
1.87 (6H, d, J = 6.5 Hz, CH(CH3)2); Diastereomer 2: 8.64-6.52
(m, Ar), 5.47 (1H, dd, J = 11.4, 6.8 Hz, central allyl), 5.23 (1H,
app t, J = 12.4 Hz, trans to phosphorus), 4.88 (1H, sept., J = 6.5
Hz, CH(CH3)2), 4.68 (1H, d, J = 10.8 Hz, trans to nitrogen), 1.71
(6H, d, J = 6.9 Hz, CH(CH3)2); 31P NMR (121 MHz): δ (CDCl3)
δ = 43.5 and 44.2 ppm; m/z ES+ (CH3OH): 782 (M+, 11), 589
(M-allyl, 67), 532 (61), 407 (58).
1
(Ar-H) cm-1; H NMR (500 MHz): δ (CDCl3) Diastereomer 1
and 2: 8.21 (d, 1H, J = 8.5 Hz), 8.1-8.05 (m, 1H, Ar-H), 8.00 (d,
1H, J = 8.3 Hz), 7.93-7.76 (m, Ar-H), 7.70 (d, J = 7.9 Hz), 7.63
(t, J = 7.4 Hz), 7.55-7.41 (m, Ar-H), 7.40-7.32 (m, Ar-H), 7.28-
7.22 (m, Ar-H), 7.2-7.14 (m, Ar-H), 7.07-7.01 (m, Ar-H), 6.99-
6.93 (m, Ar-H, Central allyl diastereomer 1), 6.88-6.84 (m, Ar-
H), 6.73 (d, J = 8.5 Hz); Diastereomer 1: 9.54 (s, 1H, H2'), 6.01
(dd, 1H, allyl trans P), 4.89 (d, 1H, J = 11.0 Hz, allyl trans N);
Diastereomer 2: 10.23 (s, 1H, H2'), 6.69-6.61 (m, central allyl),
6.22 (t, 1H, J = 10.1 Hz, allyl trans P), 5.63 (d, 1H, J = 11.9 Hz,
allyl trans N); 31P NMR (121.4 MHz): δ (CDCl3) 30.1, 29.8 ppm;
m/z (ESI / pos in CH3OH) cation: 740 = M-BF4.
[(S)-Diphenyl[1-(2-methylquinazolin-4-yl)(2-
naphthyl)]phosphine-[1,3-diphenyl-π-allyl]palladium]
tetrafluoroborate
10b.
Di-µ-chloro-bis(1,3-diphenyl-π-
allyl)dipalladium 11, (0.026 g, 0.039 mmol), (S)-diphenyl[1-(2-
methylquinazolin-4-yl)(2-naphthyl)]phosphine 7b, (0.035 g,
0.077 mmol) and sodium tetrafluoroborate (0.017 g, 0.16 mmol)
were placed in a Schlenk tube under nitrogen. Dry degassed
dichloromethane (1.6 ml) was added via syringe to give an
orange suspension which was stirred for 16 h. The solid was
removed by filtration, then diethyl ether added to precipitate an