N. Yamagiwa et al. / Tetrahedron: Asymmetry 17 (2006) 566–573
571
J(C,P) = 6.3 Hz), 127.4, 129.4 (d, J
= 5.1 Hz), 129.7,
4.3.6.
1-Cyano-3-phenylpropyl
diethyl
phosphate
;
(C,P)
3
1
ꢀ1
1
40.7;
P NMR (CDCl ) d ꢀ1.86; LRMS (ESI,
6f. Colorless oil; IR (neat) m 1274, 1032 cm
3
+
1
methanol) m/z 306 [M+Na ]; HRMS (FAB) m/z
H NMR (CDCl ) d 1.36–1.39 (m, 6H), 2.21–2.33 (m,
3
+
2
84.1050 [M+H ] calcd for C H NO P = 284.1046;
2H), 2.81–2.90 (m, 2H), 4.15–4.22 (m, 4H), 4.96–5.00
(m, 1H), 7.20–7.33 (m, 5H); C NMR (CDCl ) d 15.8
(d, J(C,P) = 3.1 Hz), 15.8 (d, J(C,P) = 3.0 Hz), 30.1, 35.6
(d, J(C,P) = 5.1 Hz), 63.9 (d, J(C,P) = 6.3 Hz), 64.5 (d,
J(C,P) = 6.1 Hz), 64.6 (d, J(C,P) = 6.3 Hz), 116.5 (d,
1
3
19
4
23:0
13
½
aꢁ ¼ þ16:5 (c 1.4, CHCl ); HPLC DAICEL CHIR-
D
3
3
ALPAK AD-H, hexane/2-propanol = 9:1, flow rate =
.0 mL/min, retention time 16.0 min (minor)/17.4 min
major).
1
(
3
1
J(C,P) = 4.1 Hz), 120.5, 128.2, 128.5, 138.8; P NMR
4
6
.3.3. 1-Cyano-1-(2-naphthyl)methyl diethyl phosphate
c. Colorless oil; IR (neat) m 1273, 1030 cm
(CDCl ) d ꢀ1.86; LRMS (ESI, methanol) m/z 320
3
ꢀ
1
+
+
;
[M+Na ]; HRMS (FAB) m/z 298.1210 [M+H ] calcd
1
23:6
H NMR (CDCl ) d 1.16 (t, J = 7.0 Hz, 3H), 1.35 (t,
for C H NO P = 298.1203; ½aꢁ ¼ þ7:4 (c 1.2,
3
14 21
4
D
J = 7.0 Hz, 3H), 3.95–4.02 (m, 2H), 4.14–4.25 (m, 2H),
CHCl ); HPLC DAICEL CHIRALPAK AD-H, hex-
3
6
7
8
.22 (d, J(H,P) = 8.9 Hz, 1H), 7.50–7.51 (m, 2H), 7.57–
ane/2-propanol = 9:1, flow rate = 1.0 mL/min, reten-
tion time 14.7 min (minor)/18.1 min (major).
.59 (m, 1H), 7.80–7.84 (m, 2H), 7.86–7.88 (m, 1H),
1
3
.00 (s, 1H);
C
NMR (CDCl3)
d
15.6 (d,
J(C,P) = 7.1 Hz), 15.8 (d, J(C,P) = 6.1 Hz), 64.4 (d,
J(C,P) = 6.1 Hz), 64.6 (d, J(C,P) = 6.3 Hz), 66.5 (d,
J(C,P) = 5.1 Hz), 116.0 (d, J(C,P) = 6.1 Hz), 123.6, 126.8,
4.3.7. 1-Cyano-2-methylpropyl diethyl phosphate 6g.
ꢀ
1 1
Colorless oil; IR (neat) m 1274, 1030 cm ; H NMR
(CDCl3) 1.10 (d, J = 7.0 Hz, 3H), 1.13 (d,
J = 6.7 Hz, 3H), 1.36–1.40 (m, 6H), 2.16–2.23 (m, 1H),
d
1
27.3, 127.4, 127.6, 128.2, 129.2, 129.4 (d,
3
1
13
J(C,P) = 5.1 Hz), 132.5, 133.7; P NMR (CDCl ) d
4.14–4.23 (m, 4H), 4.83 (dd, J = 5.5, 8.2 Hz, 1H);
C
3
+
ꢀ
1.67; LRMS (ESI, methanol) m/z 342 [M+Na ];
NMR (CDCl ) d 15.8, 15.9, 16.8, 17.2, 32.5 (d,
3
+
HRMS (FAB) m/z 320.1051 [M+H ] calcd for
J(C,P) = 6.3 Hz), 64.5 (d, J(C,P) = 4.1 Hz), 64.6 (d,
22:3
C H NO P = 320.1046; ½aꢁ ¼ þ10:8 (c 1.0, CHCl );
J(C,P) = 4.1 Hz), 69.9 (d, J
= 6.3 Hz), 115.8 (d,
1
6
19
4
D
3
(C,P)
3
1
HPLC DAICEL CHIRALPAK AD-H, hexane/2-pro-
panol = 9:1, flow rate = 1.0 mL/min, retention time
J(C,P) = 3.1 Hz); P NMR (CDCl ) d ꢀ1.58; LRMS
3
+
(ESI, methanol) m/z 258 [M+Na ]; HRMS (FAB) m/z
+
2
2.6 min (minor)/34.3 min (major).
236.1044 [M+H ] calcd for C H NO P = 236.1046;
9
19
4
2
D
3:0
½
aꢁ ¼ þ23:9 (c 1.4, CHCl ); GC, initial temp 90 ꢁC,
3
4
6
.3.4. 1-Cyano-1-(1-naphthyl)methyl diethyl phosphate
d. Colorless oil; IR (neat) m 1273, 1031, 2359 cm ;
initial time 5 min, program rate 0.5 ꢁC/min, final temp
120 ꢁC, final time 10 min, injection temp 200 ꢁC, detec-
tion temp 250 ꢁC, retention time 43.7 min (minor)/
44.7 min (major).
ꢀ
1
1
H NMR (CDCl ) d 1.06 (t, J = 7.0 Hz, 3H), 1.35 (t,
3
J = 7.0 Hz, 3H), 3.83–3.96 (m, 2H), 4.14–4.27 (m, 2H),
6
1
.64 (d, J(H,P) = 8.9 Hz, 1H), 7.45 (m, 1H), 7.52 (m,
H), 7.60 (m, 1H), 7.76 (d, J = 6.7 Hz, 1H), 7.87 (d,
4.3.8. 1-Cyano-1-cyclohexylmethyl diethyl phosphate
6h. Colorless oil; IR (neat) m 1273, 1027 cm
ꢀ
1
J = 7.9 Hz, 1H), 7.91 (d, J = 8.2 Hz, 1H), 8.22 (d,
;
1
3
1
J = 8.2 Hz, 1H);
C NMR (CDCl ) d 15.5 (d,
H NMR (CDCl ) d 1.08–1.27 (m, 6H), 1.32 (t,
3
3
J(C,P) = 7.1 Hz), 15.7 (d, J(C,P) = 6.3 Hz), 64.4 (d,
J(C,P) = 5.1 Hz), 64.7 (d, J(C,P) = 6.1 Hz), 65.1 (d,
J(C,P) = 5.1 Hz), 116.0 (d, J(C,P) = 5.1 Hz), 122.6, 124.8,
J = 6.8 Hz, 3H), 1.33 (t, J = 6.7 Hz, 3H), 1.65–1.88
(m, 6H), 4.09–4.16 (m, 4H), 4.75 (dd, J = 6.1, 8.0 Hz,
1
3
1H); C NMR (CDCl ) d 15.9 (d, J
= 2.0 Hz),
(C,P)
3
1
1
26.4, 127.1, 127.4, 127.5 (d, J
= 6.3 Hz), 128.8,
15.9 (d, J(C,P) = 3.1 Hz), 25.1, 25.1, 25.6, 27.3, 27.6,
41.4 (d, J(C,P) = 5.3 Hz), 64.5 (d, J(C,P) = 6.1 Hz), 64.5
(
C,P)
3
1
29.6, 131.5, 133.7; P NMR (CDCl ) d ꢀ1.80; LRMS
3
+
(
ESI, methanol) m/z 342 [M+Na ]; HRMS (FAB) m/z
(d, J(C,P) = 6.1 Hz), 69.2 (d, J
= 6.3 Hz), 116.0 (d,
(C,P)
+
31
3
20.1051 [M+H ] calcd for C H NO P = 320.1046;
J(C,P) = 3.1 Hz); P NMR (CDCl ) d ꢀ1.45; LRMS
1
6
19
4
3
22:9
+
½
aꢁ ¼ þ67:7 (c 1.1, CHCl ); HPLC DAICEL CHIR-
(ESI, methanol) m/z 298 [M+Na ]; HRMS (FAB) m/z
D
3
+
ALPAK AD-H, hexane/2-propanol = 9:1, flow rate =
.0 mL/min, retention time 15.7 min (minor)/23.1 min
major).
276.1362 [M+H ] calcd for C H NO P = 276.1359;
1
2
23
4
23:0
1
(
½aꢁ ¼ þ15:0 (c 1.2, CHCl ); GC, initial temp 140 ꢁC,
D
3
initial time 10 min, program rate 0.7 ꢁC/min, final temp
1
60 ꢁC, final time 20 min, injection temp 250 ꢁC, detec-
4
.3.5. 1-Cyanohexyl diethyl phosphate 6e. Colorless oil;
tion temp 250 ꢁC, retention time 36.3 min (minor)/
37.1 min (major).
ꢀ
1 1
IR (neat) m 1275, 1030 cm ; H NMR (CDCl ) d 0.89–
3
0
1
1
2
.92 (m, 3H), 1.34–1.40 (m, 10H), 1.53–1.55 (m, 2H),
.92–1.96 (m, 2H), 4.14–4.22 (m, 4H), 4.97–5.01 (m,
4.3.9. 1-Cyano-2,2-dimethyl-3-phenylpropyl diethyl phos-
phate 6i. Colorless oil; IR (neat) m 1276, 1032 cm ; H
1
3
ꢀ1
1
H); C NMR (CDCl ) d 13.7, 15.9 (d, J(C,P) = 7.1 Hz),
3
2.2, 23.7, 30.7, 34.0 (d, J(C,P) = 6.1 Hz), 64.5 (d,
NMR (CDCl ) d 1.06 (s, 3H), 1.07 (s, 3H), 1.38 (t,
3
J(C,P) = 5.1 Hz), 64.6 (d, J(C,P) = 6.3 Hz), 64.7 (d,
J = 7.0 Hz, 6H), 2.74 (s, 2H), 4.17–4.25 (m, 4H),
3
1
J(C,P) = 6.1 Hz), 116.8 (d, J(C,P) = 4.1 Hz); P NMR
CDCl ) d ꢀ1.62; LRMS (ESI, methanol) m/z 286
4.69 (d, J(H,P) = 7.7 Hz, 1H), 7.17 (d, J
2H), 7.24–7.32 (m, 3H); C NMR (CDCl ) d 15.9 (d,
= 7.3 Hz,
(H,P)
1
3
(
3
3
+
+
[
M+Na ]; HRMS (FAB) m/z 264.1364 [M+H ] calcd
J(C,P) = 6.1 Hz), 15.9 (d, J(C,P) = 6.1 Hz), 22.0, 22.3,
39.3 (d, J(C,P) = 6.3 Hz), 43.2, 64.6 (d, J(C,P) = 6.3 Hz),
2
D
3:7
for C H NO P = 264.1359; ½aꢁ ¼ þ21:0 (c 0.9,
1
1
23
4
CHCl ); GC, initial temp 110 ꢁC, initial time 10 min,
72.5 (d, J
= 7.3 Hz), 116.0, 126.7, 128.1, 130.5,
(C,P)
3
3
1
program rate 0.1 ꢁC/min, final temp 150 ꢁC, final time
136.0; P NMR (CDCl ) d ꢀ1.54; LRMS (ESI, metha-
3
+
3
0 min, injection temp 200 ꢁC, detection temp 250 ꢁC,
nol) m/z 348 [M+Na ]; HRMS (FAB) m/z 326.1521
+
retention time 89.1 min (minor)/90.9 min (major).
[M+H ]
calcd
for
C H NO P = 326.1516;
16 25 4