T. Akiyama et al. / Tetrahedron 65 (2009) 4950–4956
4955
Chiralpak AD-H (hexane/i-PrOH¼1:1/v:v), flow rate¼0.5 mL/min,
UV¼254 nm, tR (major)¼14.4 min (R), tR (minor)¼28.9 min (S).
Chiralpak AD-H (hexane/i-PrOH¼1:1/v:v), flow rate¼0.5 mL/min,
UV¼254 nm, tR (major)¼16.9 min (R), tR (minor)¼20.1 min (S).
4.8. Diisopropyl 1-[N-(4-methoxyphenyl)amino]-3-phenyl-
4.12. Diisopropyl 3-(2-chlorophenyl)-1-[N-(4-methoxy-
2-propenylphosphonate
phenyl)amino]-2-propenylphosphonate
Yellow oil. IR (CHCl3) 2986, 1512, 1240, 1209, and 995 cmꢀ1. 1H
Yellow oil. IR (CHCl3) 2984, 1512, 1240, and 997 cmꢀ1. 1H NMR
NMR (400 MHz, CDCl3)
6.70–6.64 (m, 3H), 6.29–6.22 (m, 1H), 4.80–4.70 (m, 2H), 4.30 (br s,
d
¼7.36–7.20 (m, 5H), 6.75 (d, J¼8.9 Hz),
(400 MHz, CDCl3)
d
¼7.50–6.65 (m, 9H), 6.26–6.19 (m, 1H), 4.82–
4.70 (m, 2H), 4.40–4.02 (m, 2H), 3.73 (s, 3H), 1.37–1.32 (m, 6H), 1.29
1H), 4.03 (br s, 1H), 3.77 (s, 3H), 1.34 (d, 6H, J¼6.2 Hz), 1.28–1.25 (m,
(d, 6H, J¼6.2 Hz). 13C NMR (75 MHz, CDCl3)
d
¼152.6, 140.6 (d,
6H); 13C NMR (75 MHz, CDCl3)
d
¼152.7, 140.8 (d, J¼13.1 Hz), 136.5
J¼13.8 Hz), 134.5 (d, J¼2.8 Hz), 132.9, 129.5, 129.1 (d, J¼12.5 Hz),
128.5, 127.4 (d, J¼4.2 Hz), 126.8 (d, J¼1.4 Hz), 126.7, 115.3, 114.7, 72.1
(d, J¼6.9 Hz), 71.6 (d, J¼6.9 Hz), 55.9 (d, J¼153.6 Hz), 55.7 (s), 24.3
(d, J¼3.5 Hz), 24.2 (d, J¼3.5 Hz), 24.0 (d, J¼4.8 Hz), 23.9 (d,
(d, J¼3.4 Hz),132.7 (d, J¼12.5 Hz),128.5,127.6,126.5,126.5,124.3 (d,
J¼4.9 Hz), 115.2, 114.8, 71.9 (d, J¼6.9 Hz), 71.6 (d, J¼7.6 Hz), 55.7,
55.5 (d, J¼153.5 Hz), 24.2 (d, J¼2.7 Hz), 24.1 (d, J¼3.5 Hz), 23.9 (d,
J¼5.2 Hz), 23.8 (dd, J¼5.2 Hz). 31P NMR (121 MHz, CDCl3)
d
21.3.
J¼4.8 Hz). 31P NMR (121 MHz, CDCl3)
¼20.9. Found: C, 60.30; H,
d
Found: C, 65.31; H, 7.37; N, 3.58%. Calcd for C22H30NO4P: C, 65.49;
6.64; N, 2.94%. Calcd for C22H29ClNO4P: C, 60.34; H, 6.68; N, 3.20%.
26
27
H, 7.49; N, 3.47%. [
a
]
þ72.3 (c 0.75, CHCl3) (84% ee). HPLC: Daicel
[a
]
þ55.2 (c 0.9, CHCl3) (87% ee). HPLC: Daicel Chiralpak AD-H
D
D
Chiralpak AD-H (hexane/i-PrOH¼1:1/v:v), flow rate¼0.5 mL/min,
(hexane/i-PrOH¼1:1/v:v), flow rate¼0.5 mL/min, UV¼254 nm, tR
UV¼254 nm, tR (major)¼15.1 min (R), tR (minor)¼23.0 min (S).
(major)¼21.8 min (R), tR (minor)¼25.0 min (S).
4.9. Diisopropyl 1-[N-(4-methoxyphenyl)amino]-3-(4-
4.13. Diisopropyl 1-[N-(4-methoxyphenyl)amino]-3-(2-
methylphenyl)-2-propenylphosphonate
nitrolphenyl)-2-propenylphosphonate
Yellow oil. IR (CHCl3) 2986, 1512, 1240, and 995 cmꢀ1. 1H NMR
Yellow oil. IR (CHCl3) 2995, 1512, 1348, 1240, and 997 cmꢀ1. 1H
(400 MHz, CDCl3)
4.69 (m, 2H), 4.33–4.00 (m, 2H), 3.72 (s, 3H), 2.31 (s, 3H), 1.37–1.22
(m, 12H). 13C NMR (75 MHz, CDCl3)
d
¼7.25–6.60 (m, 9H), 6.22–6.16 (m, 1H), 4.80–
NMR (400 MHz, CDCl3)
d
¼8.16–6.62 (m, 9H), 6.54–6.45 (m, 1H),
4.83–4.68 (m, 2H), 4.42–4.05 (m, 2H), 3.73 (s, 3H), 1.35 (d, 6H,
d¼152.5, 140.7 (d, J¼13.8 Hz),
J¼6.2 Hz), 1.27–1.23 (m, 6H). 13C NMR (75 MHz, CDCl3)
¼152.9,
d
137.4, 133.6 (d, J¼2.8 Hz), 132.5 (d, J¼12.5 Hz), 129.1, 126.3 (d,
J¼1.4 Hz), 123.0 (d, J¼4.8 Hz), 115.1, 114.7, 71.9 (d, J¼6.9 Hz), 71.5 (d,
J¼7.6 Hz), 55.7, 55.6 (d, J¼153.6 Hz), 24.4 (d, J¼3.5 Hz), 24.3 (d,
J¼3.5 Hz), 24.0 (d, J¼4.8 Hz), 23.9 (d, J¼4.8 Hz), 21.3. 31P NMR
140.5 (d, J¼13.8 Hz), 133.1, 132.3 (d, J¼2.8 Hz), 130.6 (d, J¼4.2 Hz),
128.8 (d, J¼2.8 Hz), 128.41, 128.2, 128.2, 124.5, 115.3, 114.8, 72.2 (d,
J¼6.9 Hz), 71.7 (d, J¼6.9 Hz), 55.8 (d, J¼152.8 Hz), 55.6, 24.2 (d,
J¼3.5 Hz), 24.0 (d, J¼3.5 Hz), 23.9 (d, J¼4.8 Hz), 23.8 (d, J¼5.6 Hz).
(121 MHz, CDCl3)
for C23H32NO4P: C, 66.17; H, 7.73; N, 3.36%. [
(86% ee). HPLC: Daicel Chiralpak AD-H (hexane/i-PrOH¼1:1/v:v),
flow rate¼0.5 mL/min, UV¼254 nm, tR (major)¼22.9 min (R), tR
(minor)¼25.6 min (S).
d
¼21.5. Found: C, 66.35; H, 7.68; N, 3.27%. Calcd
31P NMR (121 MHz, CDCl3)
d
¼20.4. Found: C, 58.87; H, 6.59; N,
26
27
a
]
þ72.7 (c 1.0, CHCl3)
6.49%. Calcd for C22H29NO6P: C, 58.92; H, 6.52; N, 6.25%. [
a
]
þ60.8
D
D
(c 1.0, CHCl3) (88% ee). HPLC: Daicel Chiralpak AD-H (hexane/
i-PrOH¼1:1/v:v), flow rate¼0.5 mL/min, UV¼254 nm, tR
(major)¼20.0 min (R), tR (minor)¼24.2 min (S).
4.10. Diisopropyl 3-(4-chlorophenyl)-1-[N-(4-methoxy-
4.14. Diisopropyl 1-[N-(4-methoxyphenyl)amino]-3-(2-
phenyl)amino]-2-propenylphosphonate
trifluoromethylphenyl)-2-propenylphosphonate
Yellow oil. IR (CHCl3) 2986, 1512, 1240, and 995 cmꢀ1. 1H NMR
Yellow oil. IR (CHCl3) 2986, 1512, 1315, 1240, 1128, and 997 cmꢀ1
1H NMR (400 MHz, CDCl3)
.
(400 MHz, CDCl3)
4.72 (m, 2H), 4.35–4.01 (m, 2H), 3.73 (s, 3H), 1.34 (d, 6H, J¼6.2 Hz),
1.28–1.25 (m, 6H). 13C NMR (75 MHz, CDCl3)
d
¼7.28–6.60 (m, 9H), 6.28–6.21 (m, 1H), 4.79–
d
¼7.60–7.04 (m, 5H), 6.76 (d, 2H,
J¼8.8 Hz), 6.66 (d, 2H, J¼8.8 Hz), 6.26–6.19 (m, 1H), 4.82–4.72 (m,
d¼152.7, 140.6 (d,
1H), 4.39–4.29 (m,1H), 4.06–4.02 (m,1H), 3.73 (s, 3H),1.89–1.21 (m,
J¼13.1 Hz), 135.0, 133.3, 131.3 (d, J¼12.4 Hz), 128.7, 127.7, 125.1 (d,
J¼5.0 Hz), 115.1, 114.8, 72.0 (d, J¼7.6 Hz), 71.6 (d, J¼7.6 Hz), 55.7,
55.4 (d, J¼153.5 Hz), 24.3 (d, J¼5.5 Hz), 24.2 (d, J¼5.5 Hz), 23.9 (d,
12H). 13C NMR (75 MHz, CDCl3)
d
¼152.8, 140.6 (d, J¼14.5 Hz), 135.6,
131.8, 129.4 (d, J¼4.2 Hz), 129.0 (d, J¼10.4 Hz), 127.5 (d, J¼34.7 Hz),
127.4, 126.0, 125.7 (d, J¼5.5 Hz), 122.4, 115.4, 114.7, 72.1 (d,
J¼6.9 Hz), 71.6 (d, J¼6.9 Hz), 55.9 (d, J¼153.5 Hz), 55.7, 24.2 (d,
J¼3.5 Hz), 24.1 (d, J¼4.1 Hz), 23.8 (d, J¼5.5 Hz), 23.7 (d, J¼5.5 Hz).
J¼5.5 Hz), 23.8 (d, J¼6.2 Hz). 31P NMR (121 MHz, CDCl3)
¼21.0.
d
Found: C, 60.48; H, 6.64; N, 3.05%. Calcd for C22H29ClNO4P: C, 60.34;
27
H, 6.68; N, 3.20%. [
a
]
þ59.4 (c 0.9, CHCl3) (83% ee). HPLC: Daicel
31P NMR (121 MHz, CDCl3)
d
¼20.7. 19F NMR (282 MHz, CDCl3)
¼1.7.
d
D
Chiralcel AD-H (hexane/i-PrOH¼1:1/v:v), flow rate¼0.5 mL/min,
Found: C, 58.84; H, 6.13; N, 2.90%. Calcd for C23H29F3NO4P: C, 58.60;
21
UV¼254 nm, tR (major)¼35.0 min (R), tR (minor)¼39.2 min (S).
H, 6.20; N, 2.97%. [
a
]
D
þ58.1 (c 0.9, CDCl3) (90% ee). HPLC: Daicel
Chiralpak AD-H (hexane/i-PrOH¼3:1/v:v), flow rate¼0.5 mL/min,
4.11. Diisopropyl 1-[N-(4-methoxyphenyl)amino]-3-(2-
methylphenyl)-2-propenylphosphonate
UV¼254 nm, tR (major)¼16.7 min (R), tR (minor)¼19.6 min (S).
4.15. Diisopropyl 1-[N-(4-methoxyphenyl)amino]-3-(1-
naphthyl)-2-propenylphosphonate
Yellow oil. IR (CHCl3) 2986, 1510, 1238, 1217, and 997 cmꢀ1
NMR (400 MHz, CDCl3)
¼7.40–6.85(m, 9H), 6.13–6.06 (m,1H), 4.81–
4.74 (m,1H), 4.36–4.05(m, 2H), 3.73(s, 3H), 2.49 (s, 3H),1.36–0.79(m,
12H). 13C NMR (75 MHz, CDCl3)
.
1H
d
Yellow oil. IR (CHCl3) 2988, 2361, 2341, 1510, 1240, and
d
¼152.5, 140.7 (d, J¼14.5 Hz), 135.6,
995 cmꢀ1. 1H NMR (400 MHz, CDCl3)
d
¼7.91–6.75 (m, 12H), 6.31–
135.3, 130.8 (d, J¼11.8 Hz), 130.0, 127.4, 125.8 (d, J¼19.4 Hz), 125.4,
125.3, 115.3, 114.6, 71.8 (d, J¼6.9 Hz), 71.4 (d, J¼7.6 Hz), 55.8 (d,
J¼154.3 Hz), 55.7, 24.1 (d, J¼5.5 Hz), 24.0 (d, J¼5.5 Hz), 24.3 (d,
6.24 (m, 1H), 4.85–4.77 (m, 2H), 4.47–4.11 (m, 2H), 3.74 (s, 3H), 1.37
(d, 6H, J¼6.2 Hz), 1.34–1.10 (m, 6H). 13C NMR (75 MHz, CDCl3)
d
¼152.6, 140.7 (d, J¼13.8 Hz), 134.3, 133.4, 130.3, 130.1, 128.3, 127.9,
J¼5.5 Hz), 24.2 (d, J¼5.5 Hz),19.8. 31P NMR (121 MHz, CDCl3)
d
¼21.4.
127.3, 127.2, 125.9, 125.5 (d, J¼14.5 Hz), 123.8, 123.8, 115.4, 114.7,
72.0 (d, J¼6.9 Hz), 71.5 (d, J¼6.9 Hz), 55.9 (d, J¼153.6 Hz), 55.8, 24.4
(d, J¼3.5 Hz), 24.3 (d, J¼3.5 Hz), 24.1 (d, J¼5.4 Hz), 24.0 (d,
Found: C, 66.29; H, 7.98; N, 3.30%. Calcd for C23H32NO4P: C, 66.17; H,
27
7.73; N, 3.36%. [
a]
þ69.5 (c 1.0, CHCl3) (82% ee). HPLC: Daicel
D