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M. Jahjah et al. / Tetrahedron: Asymmetry 18 (2007) 1224–1232
H2O2 10% (7 mL) were added at 0 ꢁC. The mixture was
stirred at room temperature for 8 h, then poured into water
(10 mL). The organic layer was washed with a saturated
solution of sodium bisulfite (1 mL) and extracted with
dichloromethane (3 · 20 mL). Solvents were evaporated
under reduced pressure and the dark yellow residue was
purified by flash chromatography on silica gel (SiO2, cyclo-
hexane/ethyl acetate 6/4) to afford pure 6 as a yellow solid
and 7 as a yellow solid (0.85 g and 0.89 g, 31% and 33%,
respectively) with a global yield of 65%.
(OCH3), 55.5 (OCH3), 97.2, 105.4, 125.1, 125.2, 125.3,
126.7, 127.1, 127.5, 127.6, 127.7, 128.0, 128.0, 128.1,
128.2, 128.5, 128.7, 128.9, 131.2, 131.3, 132.5, 132.7,
132.9, 133.1, 133.2, 133.7, 133.8, 134.4, 134.5, 134.6,
134.7, 134.8, 134.9, 143.4, 143.5, 160.2, 162.8, 163.6; 31P
NMR (81 MHz, CDCl3): d = +27.0 (s); MS (ESI): m/z:
515.2 [M+H]+; Elemental Anal. Calcd for C34H27O3P
(515.2): C, 79.36; H, 5.29; P, 6.02. Found: C, 79.00; H,
6.17; P, 5.37; mp 199 ꢁC; Rf = 0.52 (cyclohexane/ethyl ace-
25
tate 4/6); ½aꢁD ¼ ꢀ30:25 (c 0.79, CH2Cl2).
1
1
Compound 6: H NMR (300 MHz, CDCl3): d = 3.41 (s,
Compound 11: H NMR (300 MHz, CDCl3): d = 3.60 (s,
3H, OCH3), 6.05 (dd, J = 8.31, 5.88 Hz, 1ArH), 6.50 (td,
J = 7.53, 1.14 Hz, 1ArH), 6.83–6.93 (m, 2ArH), 7.05 (td,
J = 8.28, 1.32 Hz, 1ArH), 7.20 (td, J = 3.21, 1.89 Hz,
1ArH), 7.23–7.28 (m, 4ArH), 7.33–7.39 (m, 4ArH), 7.42
(t, J = 6.78 Hz, 2ArH), 7.47–7.54 (m, 2ArH), 7.88–7.92
(m, 4ArH); 13C NMR (75 MHz, CDCl3): d = 54.4
(OCH3); 109,2; 109.3; 119.1; 120.4; 120.5; 125.1; 125.2;
125.3; 126.8; 127.0; 127.6; 127.8; 128.1; 128.1; 128.2;
128.4; 128.5; 129.0; 131.4; 131.4; 132.3; 132.4; 132.6;
132.8; 132.9; 133.1; 133.4; 133.5; 133.6; 133.8; 134.6;
134.7; 134.8; 143.6; 158.7; 31P NMR (81 MHz, CDCl3):
d = 27.1 (s); MS (ESI): m/z: 485.2 [M+H]+; Elemental
Anal. Calcd for C33H24O2P (484.16): C, 81.80; H, 5.2; P,
3H, OCH3), 3.81 (s, 3H, OCH3), 6.26 (dd, J = 4.71,
2.07 Hz, 1ArH), 5.42 (td, J = 8.46, 1.68 Hz, 1ArH), 6.84
(td, J = 7.74, 3.03 Hz, 2ArH), 6.99 (td, J = 6.03, 3.21 Hz,
1ArH), 7.03 (d, J = 7.71 Hz, 1ArH), 7.15 (td, J = 6.78,
3 Hz, 2ArH), 7.23 (td, J = 6.6, 1.14 Hz, 1ArH), 7.33 (td,
J = 8.07, 1.14 Hz, 2ArH), 7.39 (dd, J = 12.46, 1.32 Hz,
1ArH), 7.42 (d, J = 12.6 Hz, 1ArH), 7.51 (d, J = 6.6 Hz,
2ArH), 7.53–7.68 (m, 3ArH), 7.77–7.84 (m, 1ArH), 7.92–
7.97 (m, 2ArH); 13C NMR (75 MHz, CDCl3): d = 55.3
(OCH3), 55.7 (OCH3), 98.6, 98.7, 105.4, 105.5, 125.0,
125.5, 125.7, 126.8, 127.0, 127.2, 127.4, 127.6, 127.7,
127.8, 128.1, 128.2, 128.8, 128.9, 129.0, 130.2, 130.3,
130.4, 131.1, 131.2, 133.1, 133.2, 133.6, 133.8, 134.8,
134.8, 135.0, 135.1, 136.2, 136.3, 143.4, 161.6; 31P NMR
(81 MHz, CDCl3): d = +28.0 (s); MS (ESI): m/z: 515.2
[M+H]+; Elemental Anal. Calcd for C34H27O3P (515.2):
C, 79.36; H, 5.29; P, 6.02. Found: C, 79.85; H, 5.99; P,
6.39. Found: C, 82.40; H, 5.65; P, 6.5; mp 190 ꢁC;
25
Rf = 0.45 (cyclohexane/ethyl acetate 5/5); ½aꢁD ¼ ꢀ33:3 (c
0.75, CH2Cl2).
1
Compound 7: H NMR (300 MHz, CDCl3): d = 3.63 (s,
6.02; mp 171 ꢁC; Rf = 0.16 (cyclohexane/ethyl acetate, 4/
25
3H, OCH3), 6.76 (dd, J = 8.07, 5.46 Hz, 1ArH), 6.84 (td,
J = 7.71, 3 Hz, 2ArH), 6.94 (td, J = 7.53, 1.14 Hz,
1ArH), 7.00 (td, J = 7.14, 1.32 Hz, 1ArH), 7.09 (d,
J = 8.1, 1ArH), 7.22–7.41 (m, 8ArH), 7.51–7.70 (m,
2ArH), 7.71–7.79 (m, 2ArH), 7.91–7.96 (m, 4ArH); 13C
NMR (75 MHz, CDCl3): d = 55.33 (OCH3); 111.0; 121.2;
121.3; 125.0; 125.5; 125.8; 126.9; 127.0; 127.2; 127.4;
127.6; 127.8; 127.9; 128.1; 128.2; 128.7; 128.9; 128.9;
130.3; 130.4; 130.6; 131.6; 131.2; 133.1; 133.3; 133.6;
133.7; 133.8; 134.7; 134.8; 134.9, 135; 135.1; 143.4; 143.5;
160.1; 31P NMR (81 MHz, CDCl3): d = 28.1 (s); MS
(ESI): m/z: 485.2 [M+H]+; Elemental Anal. Calcd for
C33H24O2P (484.16): C, 81.80; H, 5.2; P, 6.39. Found: C,
6); ½aꢁD ¼ ꢀ38:0 (c 0.79, CH2Cl2).
4.2.3. Phosphine oxides 8 and 9
4.2.3.1. (R)-2(R or S)[(-2-Hydroxyphenyl)phenylphosphin-
yl]-1,10-binaphthyl 8.
A
solution of
6
(200 mg,
0.41 mmol) in dry dichloromethane (4 mL) was cooled at
0 ꢁC. A 1 M solution of BBr3 in dichloromethane
(1.2 mL, 1.2 mmol) was added and the reaction mixture
stirred at 0 ꢁC for 1 h, then at room temperature for
24 h. The solution was cooled to 5 ꢁC and methanol
(3 mL) was carefully added. After removal of the organic
solvents, the residue was dissolved in dichloromethane
(1 mL) and the solution was passed through a short column
of silica gel. The filtrate was concentrated to give 8
(195 mg, 100%) as a grey solid.
79.70; H, 6.51; P, 5.86; mp 103–105 ꢁC; Rf = 0.46 (cyclo-
25
hexane/ethyl acetate 5/5); ½aꢁD ¼ ꢀ63:1 (c 0.75, CH2Cl2).
4.2.2.2. (R)-2(R or S)[(-2,4-dimethoxyphenyl)phenylphos-
phinyl]-1,10-binaphthyl 10 and 11. These were obtained by
the same procedure from 4 (1.28 g, 5.20 mmol) and purified
by flash chromatography (SiO2, cyclohexane/ethyl acetate
5/5) affording 10 (0.6 g, 45%) and 11 (0.54 g, 41%) as yel-
1H NMR (300 MHz, CDCl3): d = 6.10 (td, J = 7.14,
2.07 Hz, 1ArH), 6.40 (dd, J = 7.92, 4.89 Hz, 1ArH),
6.78–6.83 (m, 2ArH), 7.01–7.09 (m, 2ArH), 7.24 (t,
J = 7.14 Hz, 1ArH), 7.32–7.36 (m, 2ArH), 7.38–7.52 (m,
6ArH), 7.68–7.81 (m, 3ArH), 7.85–7.93 (m, 4ArH), 7.42
(s, 1H, OH); 13C NMR (75 MHz, CDCl3): d = 110,4;
111.8; 117.7; 117.8; 118.8; 119.0; 125.4; 125.9; 126.0;
127.2; 127.5; 128.2; 128.3; 128.4; 128.5; 128.7; 128.8;
128.9; 129.0; 129.1; 129.2; 130.4; 130.5; 132.1; 132.2;
132.3; 132.4; 132.8; 132.9; 132.9; 133.3; 133.6; 133.8;
134.0; 134.6; 134.7; 135.2; 135.3; 146.0; 146.1; 162.4; 31P
NMR (81 MHz, CDCl3): d = +39.9 (s); MS (ESI): m/z:
471.2 [M+H]+; Elemental Anal. Calcd for C32H23O2P
1
low solids with a global yield of 86%. Compound 10: H
NMR (300 MHz, CDCl3): d = 3.30 (s, 3H, OCH3), 3.53
(s, 3H, OCH3), 5.52 (dd, J = 4.89, 2.07 Hz, 1ArH), 5.91
(td, J = 8.67, 1.86 Hz, 1ArH), 6.79 (d, J = 8.28 Hz,
1ArH), 6.97 (td, J = 6.96, 1.32 Hz, 1ArH), 7.02 (d,
J = 4.71 Hz, 1ArH), 7.03–7.05 (m, 1ArH), 7.11 (dd,
J = 7.71, 1.11 Hz, 1ArH), 7.12–7.21 (m, 2ArH), 7.24 (dd,
J = 6.96, 3.0 Hz, 1ArH), 7.28 (dd, J = 8.10, 5.28 Hz,
1ArH), 7.35–7.43 (m, 1ArH), 7.53 (td J = 8.1, 6.0 Hz,
2ArH), 7.57–7.67 (m, 2ArH), 7.78–7.82 (m, 4ArH), 7.93
(s, 1ArH); 13C NMR (75 MHz, CDCl3): d = 54.4
(471.2): C, 81.69; H, 4.93; P, 6.58. Found: C, 81.65; H,
25
5.12; P, 6.48; mp 197 ꢁC; ½aꢁD ¼ ꢀ19:6 (c 0.72, CH2Cl2).