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Z. Zhou et al. / Journal of Organometallic Chemistry 691 (2006) 5790–5797
1.29(t, 6H, J = 7.0 Hz, 2CH3), 1.57–2.20(m, 12H, 6CH2),
2.54(s, 1H, OH), 3.50(m, 1H, CH), 3.80(m, 1H, CH),
4.14(m, 4H, 2CH2O). Anal. Calc. for C12H25O3PS2: C,
46.13; H, 8.07. Found: C, 46.06; H, 7.92%. HPLC condi-
tions: OD column, hexane:isopropanol = 90:10, flow rate
0.8 mL/min, tR = 5.58 and 6.89 min.
For 7d: R = Ph, 53% yield, 29% ee. 31P NMR(d,
CDCl3): 92.36; 1H NMR(d, CDCl3): 1.20(t, 3H,
J = 6.9 Hz, 2CH3), 1.28(t, 3H, J = 6.9 Hz, CH3),
2.03(broad, 1H, OH), 3.95(d, 2H, J = 6.9 Hz, CH2),
3.84–4.20(m, 4H, 2CH2O), 4.40(dt, 1H, J = 6.9 Hz, JP–H
= 14.4 Hz, CHS), 7.26–7.36(m, 5Harom). Anal. Calc. for
C12H19O3PS2: C, 47.04; H, 6.25. Found: C, 47.01; H,
6.32%. HPLC conditions: AD column, hexane:isopropa-
nol = 98:2, flow rate 0.8 mL/min, tR = 10.87 and
12.13 min.
3.10. Ring-opening of racemic epoxides with O,O-diethyl
dithiophosphoric acid (general procedure)
To a 25 mL of 4-necked flask was placed 0.1 mmol of
chiral salen ligand, 5 mL of dry toluene, and 0.1 mmol of
Ti(OPr-i)4 at room temperature under a nitrogen atmo-
sphere. After stirring for 1 h, 1 mmol of dithiophosphorus
acid was added dropwise to the resulting mixture. The
reaction was stirred for additional 0.5 h. Then 1 mmol
of epoxide was added and the whole was stirred for 5–
10 min (monitored by TLC). After removal of solvent,
the crude product was analyzed by 31P NMR, and then
purified by column chromatography on silica gel (200–
300 mesh, gradient eluted with petroleum ether/ethyl ace-
tate) to provide the ring-opening product 6 and 7. The ee
value of the product was determined by chiral HPLC
analysis.
For 6e: R = m-ClC6H4, 32% yield, 35% ee. 31P NMR(d,
CDCl3): 95.31; 1H NMR(d, CDCl3): 1.37(t, 6H,
J = 6.9 Hz, 2CH3), 2.58(broad, 1H, OH), 3.02–3.28(m,
2H, CH2S), 4.10–4.28(m, 4H, 2CH2O), 4.91(dd, 1H,
J = 3.6 and 3.9 Hz, CHO), 7.23–7.40(m, 4Harom). Anal.
Calc. for C12H18ClO3PS2: C, 42.29; H, 5.32. Found: C,
42.19; H, 5.26%. HPLC conditions: AD column, hex-
ane:isopropanol = 90:10, flow rate 1.0 mL/min, tR = 7.34
and 8.59 min.
For 7e: R = m-ClC6H4, 41% yield, 47% ee. 31P NMR(d,
CDCl3): 91.71; 1H NMR(d, CDCl3): 1.23(t, 3H,
J = 6.9 Hz, CH3), 1.29(t, 3H, J = 6.9 Hz, CH3),
2.13(broad, 1H, OH), 3.94(d, 2H, J = 6.9 Hz, CH2O),
4.08–4.19(m, 4H, 2CH2O), 4.41(dt, 1H, J = 6.9 Hz,
JP–H = 13.8 Hz, CHS), 7.25–7.37(m, 4Harom). Anal. Calc.
for C12H18ClO3PS2: C, 42.29; H, 5.32. Found: C, 42.31;
H, 5.29%. HPLC conditions: AS column, hexane:isopropa-
nol = 99:1, flow rate 0.8 mL/min, tR = 40.21 and
42.56 min.
For 6a: R = Et, 82% yield, n2D0 1:5138. 31P NMR(d,
CDCl3): 95.45; 1H NMR(d, CDCl3): 0.96(t, 3H,
J = 7.1 Hz, CH3), 1.31(t, 6H, J = 7.1 Hz, 2CH3), 1.52(m,
2H, CH2), 2.24(broad, 1H, OH), 3.10(m, 2H, CH2),
3.72(m, 1H, CH), 4.13(m, 4H, 2CH2O). Anal. Calc. for
C8H19O3PS2: C, 37.21; H, 7.36. Found: C, 37.19; H,
7.42%. HPLC conditions: OJ column, hexane:isopropa-
nol = 90:10, flow rate 0.8 mL/min, tR = 6.75 and 7.16 min.
For 6b: R = n-Pr, 52% yield, 24% ee. 31P NMR(d,
For 6f: R = m-MeOC6H4, 49% yield, 54% ee. 31P
1
NMR(d, CDCl3): 95.43; H NMR(d, CDCl3): 1.36(t, 6H,
J = 6.9 Hz, 2CH3), 2.51(broad, 1H, OH), 3.05–3.33(m,
2H, CH2S), 3.81(s, 3H, CH3O), 4.09–4.28(m, 4H,
2CH2O), 4.90(dd, 1H, J = 3.6 and 3.9 Hz, CHO), 6.82–
7.30(m, 4Harom). Anal. Calc. for C13H21O4PS2: C, 46.41;
H, 6.29. Found: C, 46.29; H, 6.31%. HPLC conditions:
AS column, hexane:isopropanol = 92:8, flow rate 0.8 mL/
min, tR = 15.62 and 18.31 min.
1
CDCl3): 95.65; H NMR(d, CDCl3): 0.91(t, 3H, J = 7.1
Hz, CH3), 1.34(t, 6H, J = 7.1 Hz, 2CH3), 1.30–1.59(m,
4H, 2CH2), 2.50(broad, 1H, OH), 2.80–3.15(m, 2H,
CH2), 3.80(m, 1H, CH), 4.18(m, 4H, 2CH2O). Anal. Calc.
for C9H21O3PS2: C, 39.69; H, 7.77. Found: C, 39.75; H,
7.65%. HPLC conditions: OJ column, hexane:isopropa-
nol = 90:10, flow rate 0.8 mL/min, tR = 7.03 and 8.21 min.
For 6c: R = CH2Cl, 78% yield, 3% ee. 31P NMR(d,
CDCl3): 96.21; 1H NMR(d, CDCl3): 1.37(t, 6H,
J = 6.9 Hz, 2CH3), 2.67(broad, 1H, OH), 3.08–3.18(m,
2H, CH2), 3.60–3.72(m, 2H, CH2), 4.14–4.19(m, 1H,
CH), 4.20(m, 4H, 2CH2O). Anal. Calc. for C7H16ClO3PS2:
C, 30.16; H, 5.79. Found: C, 29.89; H, 5.81%. HPLC con-
ditions: AD-H column, hexane:isopropanol = 92:8, flow
rate 0.8 mL/min, tR = 9.10 and 9.51 min.
For 7f: R = m-MeOC6H4, 23% yield, 41% ee. 31P
1
NMR(d, CDCl3): 92.12; H NMR(d, CDCl3): 1.22(t, 3H,
J = 6.9 Hz, CH3), 1.29(t, 3H, J = 6.9 Hz, CH3),
2.26(broad, 1H, OH), 3.80(s, 3H, CH3O), 3.92(d, 2H,
J = 6.9 Hz, CH2O), 4.03–4.20(m, 4H, 2CH2O), 4.39(dt,
1H, J = 6.9 Hz, JP–H = 14.1 Hz, CHS), 6.81–7.28(m,
4Harom). Anal. Calc. for C13H21O4PS2: C, 46.41; H, 6.29.
Found: C, 46.45; H, 6.38%. HPLC conditions: AS-H col-
umn, hexane:isopropanol = 90:10, flow rate 0.9 mL/min,
tR = 10.34 and 11.31 min.
For 6d: R = Ph, 21% yield, 55% ee. 31P NMR(d,
CDCl3): 95.71; 1H NMR(d, CDCl3): 1.24(t, 6H,
J = 7.1 Hz, 2CH3), 2.44(broad, 1H, OH), 2.93-3.21(m,
2H, CH2S), 4.04(m, 4H, 2CH2O), 4.80(dd, 1H, J = 3.6
and 3.9 Hz, CHO), 7.18–7.26(m, 5Harom). Anal. Calc. for
C12H19O3PS2: C, 47.04; H, 6.25. Found: C, 46.98; H,
6.21%. HPLC conditions: AD column, hexane:isopropa-
nol = 95:5, flow rate 1.0 mL/min, tR = 15.94 and
17.47 min.
For 6g: R = m-O2NC6H4, 41% yield, 24% ee. 31P
1
NMR(d, CDCl3): 95.66; H NMR(d, CDCl3): 1.37(t, 6H,
J = 6.9 Hz, 2CH3), 3.07(broad, 1H, OH), 3.10–3.39(m,
2H, CH2S), 4.10–4.28(m, 4H, 2CH2O), 5.09(dd, 1H,
J = 3.6 and 3.9 Hz, CHO), 7.55(d, J = 7.8 Hz, 1Harom),
7.76(d, J = 7.8 Hz, 1Harom), 8.12(d, J = 7.8 Hz, 1Harom),
8.28(s, 1Harom). Anal. Calc. for C12H18NO5PS2: C, 41.02;
H, 5.16; N, 3.99. Found: C, 41.13; H, 5.20; N, 4.01%.
HPLC conditions: OD column, hexane:isopropa-