M. McCarthy et al. / Tetrahedron: Asymmetry 10 (1999) 2797–2807
2805
(0.830 g, 7.4 mmol) in DMF (6 ml) was added. The resulting black solution was kept at 100°C and
an additional portion of diphenylphosphine (0.185 ml, 1.06 mmol) was added after 1 h. The reaction
was kept at 100°C under nitrogen for 3 days. The solvent was removed in vacuo (40°C on a vacuum
line). The product was purified by silica gel flash column chromatography (hexane:ethyl acetate 2:1)
to give (R,S) diphenyl[1-(2-phenylquinazolin-4-yl)(2-naphthyl)]phosphine (0.710 g, 74.4%) as a white
solid, m.p. 218–219°C. Found: C, 83.3; H, 4.9; N, 5.4. C36H25N2P requires: C, 83.7; H, 4.9; N, 5.4%;
1H NMR (500 MHz): δ (CDCl3) 8.19 (m, 3H, H8+o-Ph), 7.96 (d, 1H, J=8.8 Hz, H4), 7.93 (d, 1H, J=8.3
0
0
Hz, H5 ), 7.87 (dt, 1H, J1=6.8 Hz, J2=1.95 Hz, H7), 7.51 (dt, 1H, J1=6.8 Hz, J2=1.5 Hz, H6 ), 7.42 (dd,
1H, JH,H=8.8 Hz, JP,H =2.9 Hz, H3), 7.40–7.39 (m, 2H, Ar-H), 7.36–7.32 (m, 3H, m-Ph, H6), 7.32–7.25
(m, 9H, H7+Ar-H) and 7.21–7.15 (m, 3H, H8 +H5 +Ar-H); 13C NMR (125.7 MHz): δ (CDCl3) 169.3
0
0
0
(d, JP,C =6.6 Hz, C4 ), 160.5 (4°C), 151.2 (4°C), 142.1 (d, JP,C =32 Hz, C2), 138.2 (4°C), 137.6–136.7
(m, i+i0), 134.8 (d, JP,C =15.3 Hz, C1), 133.8 (CH), 133.8 (CH), 133.7 (C7), 133.7–133.5 (CH), 132.0 (d,
JP,C =7.1 Hz, C9), 130.2 (d, JP,C =13.7 Hz, C3), 129.2 (d, JP,C =10.7 Hz, C4), 128.9 (C8+o-Ph), 128.5–128.3
0
0
(CH), 128.2 (C5 ), 127.1 (CH), 127.0 (CH), 126.9 (C6 ), 126.5 (C5), 126.5 (CH), 124.1 (4°C) and 124.0
(4°C); 31P NMR (101.3 MHz): δ (CDCl3) −12.4; νmax (KBr): 3054 (w) (Ar-H), 1614 (m) (Ar-H), 1584
(m) (Ar-H), 1568 (m) (Ar-H), 1435 (m) (P-Ph), 711 (s) (Ar-H) and 697 (s) (Ar-H) cm−1; m/z (EIMS 70
eV) 516 (M+, 62%), 439 (100), 362 (5) and 77 (15).
4.5. Resolution of diphenyl[1-(2-phenylquinazolin-4-yl)(2-naphthyl)]phosphine
A mixture of diphenyl[1-(2-phenylquinazolin-4-yl)(2-naphthyl)]phosphine (0.616 g, 1.19 mmol)
and (+)di-µ-chlorobis[(R)-dimethyl(1-(1-naphthyl)ethyl)aminato-C2,N]dipalladium(II) (0.406 g, 0.597
mmol) in methanol (35 ml) was stirred at room temperature overnight. The reagents slowly dissolved,
but after 15 min a white solid precipitated from the solution. The solid was filtered off, washed with
methanol (10 ml) and dried, to give a white solid. The solution was concentrated to dryness. To the
residue was added methanol (8 ml) and the mixture was stirred for 1 h. The solid was filtered off, washed
with methanol (20 ml), and dried to give more white solid. The solids were combined to give (R,R)-16
(0.414 g, 81%), as its chloride salt. The filtrate was reduced in vacuo, butanone (5 ml) and diethyl ether
(10 ml) were added and a solid precipitated upon standing (2 days). The solid was filtered off, washed
with diethyl ether (10 ml) to give (S,S)-16 (0.318 g, 62%).
Complex (R,R)-16, m.p. 211–212°C; [α]21 94.2 (c 0.6, CHCl3). Found: C, 69.9; H, 4.7; N, 4.85; Cl,
D
1
4.0. C50H41N3ClPPd requires: C, 70.0; H, 4.8; N, 4.9; Cl, 4.1%; H NMR (500 MHz): δ (CDCl3) 8.45
(d, 2H, J=7.33 Hz), 7.96 (d, 1H, J=8.3 Hz), 7.92 (d, 1H, J=7.8 Hz), 7.89 (d, 1H, J=8.3 Hz), 7.86–7.82 (m,
2H), 7.73 (dt, 1H), 7.57 (d, 1H, J=8.3 Hz), 7.53–7.19 (m, 15H), 6.97 (br, 2H), 6.77 (d, 1H, J=8.8 Hz),
6.13 (br, 1H), 5.99 (dd, 1H, J1=8.8 Hz, J2=2.44 Hz), 4.11 (quin, 1H, J=6.4 Hz, CHMe), 2.83 (d, 3H, J=2.9
Hz, NCH3), 1.97 (d, 3H, J=5.9 Hz, CHMe) and 1.94 (s, 3H, NCH3); 13C NMR (125.7 MHz): δ (CDCl3)
168.2, 160.0, 151.1, 148.3, 138.3, 138.2, 136.0, 135.9, 135.8, 133.8, 133.6, 132.5, 131.2, 130.5–128.3,
128.2, 128.0, 127.9, 127.3, 127.1, 127.0, 126.9, 126.8, 126.5, 125.2, 124.4, 123.7, 123.1, 72.9 (CH), 50.4
(NCH3), 48.6 (NCH3) and 23.5 (CCH3); 31P NMR (101.3MHz): δ (CDCl3) 40.0 ppm; νmax (CH2Cl2):
3049 (Ar-H), 1614 (m) (Ar-H), 1565 (m) (Ar-H), 1543 (m) (Ar-H), 1436 (P-Ph) and 812 (Ar-H) cm−1;
m/z (ESI/pos in CH3OH) cation 821=M−Cl.
Complex (S,S)-16, m.p. 199–200°C; [α]21 −96.8 (c 1.4, CHCl3). Found: C, 69.9; H, 4.8; N, 4.8; Cl,
D
4.0. C50H41N3ClPPd requires: C, 70.0; H, 4.8; N, 4.9; Cl, 4.1%; 1H NMR (500 MHz): δ (CDCl3) 8.32 (t,
1H), 8.17 (d, 2H, J=8.5 Hz), 8.02 (d, 1H, J=8.5 Hz), 7.90 (t, 3H), 7.78 (br t, 3H), 7.72 (t, 1H), 7.62 (d, 1H,
J=8.6 Hz), 7.54 (d, 1H, J=7.9 Hz), 7.49–7.24 (m, 11H), 7.16 (t, 1H), 6.79 (d, 1H, J=8.54 Hz), 6.72 (d, 1H,
J=8.8 Hz), 6.68 (br d, 1H, J=7.0 Hz), 6.56 (br t, 2H), 6.45 (br, 1H), 4.20 (quin, 1H, J=6.1 Hz, CHMe),