PAPER
Metal Triflate-Catalyzed One-Pot Synthesis of a-Aminophosphonates
2695
2
1
-OCH CH ), 108.89, 113.74, 120.31, 128.74–130.62, 135.76, Anal. Calcd for C H ClNO P: C, 57.79; H, 5.95. Found: C, 57.75;
2
3
17 21
3
50.08 (C H , C H ).
H, 5.93.
6
5
6
4
+
MS (70 eV): m/z = 364 [M ], 227 [M – P(O)(OEt) ].
2
Compound h
IR: 3303 (NH) cm .
Anal. Calcd for C H N O P: C, 56.04; H, 5.77. Found: C, 56.10;
H, 5.73.
–1
1
7
21
2
5
1
2
H NMR (CDCl , TMS): d = 1.15 (t, J = 7.0 Hz, 3 H, 2-
3
HH
3
OCH CH ), 1.31 (t, J = 7.0 Hz, 3 H, 2-OCH CH ), 2.21 (s, 3 H,
2
3
HH
2
3
Compound d
IR: 3286 (NH) cm .
–
1
CH
3
), 3.70–3.76 (m, 1 H, 2-OCH CH ), 3.95–4.02 (m, 1 H, 2-
2
3
1
OCH CH ), 4.11–4.20 (m, 2 H, 2-OCH CH ), 4.77 (d, J = 24.4
2
3
2
3
PH
1
2
H NMR (CDCl , TMS): d = 1.04 (t, J = 7.1 Hz, 3 H, 2-
2
3
HH
Hz, 1 H, CH), 6.55 (d, J = 8.2 Hz, 2 H, C H , C H ), 6.94 (d,
HH 6 4 6 5
OCH CH ), 1.18–1.32 (m, 3 H, 2-OCH CH ), 3.56–3.63 (m, 1 H, 2-
2
2
3
2
3
JHH = 8.1 Hz, 2 H, C H , C H ), 7.29–7.38 (m, 3 H, C H , C H ),
6 4 6 5 6 4 6 5
OCH CH ), 3.83–3.92 (m, 1 H, 2-OCH CH ), 4.05–4.12 (m, 2 H, 2-
2
3
2
3
7.48–7.51 (m, 2 H, C H , C H ).
6 4 6 5
2
1
OCH CH ), 4.72 (dd, J = 7.9 Hz, J = 25.4 Hz, 1 H, CH), 6.79–
2
3
HH
PH
13
3
C NMR (CDCl , TMS): d = 16.59 (d, J = 5.8 Hz, 2-OCH CH ),
3
CP
2
3
6
.83 (m, 1 H, C H , C H ), 7.10–7.43 (m, 8 H, C H , C H ).
6 4 6 5 6 4 6 5
3
1
1
6.83 (d, J = 5.8 Hz, 2-OCH CH ), 56.71 (d, J = 150.4 Hz,
CP 2 3 CP
1
3
3
C NMR (CDCl , TMS): d = 15.15 (d, J = 5.7 Hz, 2-OCH CH ),
3
CP
2
3
CH), 63.56–63.72 (2-OCH CH ), 114.37, 127.99–130.06, 136.43,
144.24–144.48 (C H , C H ).
2
3
3
1
1
5.42 (d, J = 5.8 Hz, 2-OCH CH ), 54.78 (d, J = 151.9 Hz,
CP
2
3
CP
2
6
5
6
4
2
CH), 62.27 (d, J = 7.2 Hz, 2-OCH CH ), 62.68 (d, J = 7.0 Hz,
CP
2
3
CP
+
MS (70 eV): m/z = 333 [M ], 196 [M – P(O)(OEt) ].
2
2
-OCH CH ), 106.96, 111.83, 118.42, 119.56, 126.82–128.70
2 3
(
C H , C H ).
Anal. Calcd for C H NO P: C, 64.86; H, 7.21. Found: C, 64.82; H,
6
5
6
4
18 24
3
+
7.19.
MS (70 eV): m/z = 364 [M ], 227 [M – P(O)(OEt) ].
2
Anal. Calcd for C H N O P: C, 56.04; H, 5.77. Found: C, 56.08;
H, 5.81.
1
7
21
2
5
Compound i
IR: 3301 (NH) cm .
–1
1
2
H NMR (CDCl , TMS): d = 1.13 (t, J = 6.8 Hz, 3 H, 2-
3
HH
Compound e
IR: 3313 (NH) cm .
2
–
1
OCH
2
CH ), 1.33 (t, JHH = 6.8 Hz, 3 H, 2-OCH CH ), 3.63–3.75 (m,
3
2
3
1
H, 2-OCH C.H ), 3.90–4.06 (m, 1 H, 2-OCH CH ), 4.14–4.21 (m,
2
3
2
3
1
H NMR (CDCl , TMS): d = 1.12–1.36 [m, 15 H, 2-OCH CH ,
3
2
3
2 H, 2-OCH CH ), 4.92–5.04 (m, 1 H, CH), 6.66–6.75 (m, 3 H,
C H , C H ), 7.10–7.16 (m, 2 H, C H , C H ), 7.48–7.67 (m, 3 H,
10 7 6 5 10 7 6 5
C H , C H ), 7.85 (s, 3 H, C H , C H ), 7.98 (s, 1 H, C H , C H ).
13
2 3
C(CH ) ], 2.92 (br s, 1 H, NH), 3.89–4.04 (m, 4 H, 2-OCH CH ),
4
H, C H ).
3
3
2
3
2
1
.95 (dd, J = 3.7 Hz, J = 11.5 Hz, 1 H, CH), 7.24–7.64 (m, 5
HH
PH
10 7 6 5 10 7 6 5 10 7 6 5
6
5
3
C NMR (CDCl , TMS): d = 16.63 (d, J = 5.8 Hz, 2-OCH CH ),
3
CP
2
3
+
MS (70 eV): m/z = 299 [M ], 162 [M – P(O)(OEt) ].
3
1
2
16.87 (d, J = 5.8 Hz, 2-OCH CH ), 56.7 (d, J = 150.1 Hz, CH),
6
1
CP 2 3 CP
2
3.73 (d, J = 7.0 Hz, 2-OCH CH ), 114.30, 118.86, 126.0–
CP 2 3
Anal. Calcd for C H NO P: C, 60.20; H, 8.69. Found: C, 60.22; H,
8
15
26
3
29.60, 133.51–133.95, 146.63–146.87 (C H , C H ).
.71.
10
7
6
5
+
MS (70 eV): m/z = 369 [M ], 232 [M – P(O)(OEt) ].
2
Compound f
IR: 3303 (NH) cm .
–
1
Anal. Calcd for C21
.45.
H24NO
3
P: C, 68.29; H, 6.50. Found: C, 68.24; H,
6
1
H NMR (CDCl , TMS): d = 1.02–1.08, (m, 3 H, 2-OCH CH ),
3
2
3
1
3
.18–1.22 (m, 3 H, 2-OCH CH ), 3.70 (s, 3 H, CH ), 3.63–3.69,
2 3 3
Compound j
IR: 3402 (NH) cm .
1
.84–3.89, 4.01–4.06 (m, 4 H, 2-OCH CH ), 4.63 (d, J = 20.8
–1
2
3
PH
Hz, 1 H, CH), 6.50–6.63 (m, 3 H, C H , C H ), 6.77–6.81 (m, 2 H,
C H , C H ), 7.00–7.03 (m, 2 H, C H , C H ), 7.29–7.31 (m, 2 H,
C H , C H ).
1
6
4
6
5
1
2
H NMR (CDCl , TMS): d = 1.16 (t, J = 7.0 Hz, 3 H, 2-
3
HH
6
4
6
5
6
4
6
5
2
OCH CH ), 1.27 (t, J = 7.0 Hz, 3 H, 2-OCH CH ), 3.98–4.13 (m,
2
3
HH
2
3
6
4
6
5
2
1
4
H, 2-OCH CH ), 4.78 (dd, J = 7.4 Hz, J = 24.5 Hz, 1 H,
2 3 HH PH
3
3
C NMR (CDCl , TMS): d = 16.66 (d, J = 5.8 Hz, 2-OCH CH ),
2
2
3
CP
2
3
CH), 6.45 (d, J = 8.1 Hz, 1 H, C H , C H ), 6.61 (t, J = 7.5
Hz, 1 H, C H , C H ), 6.93–6.96 (m, 1 H, C H , C H ), 7.23–7.47
6 4 6 5 6 4 6 5
(m, 6 H, C H , C H ).
13
HH 6 4 6 5 HH
3
1
1
6.84 (d, J = 5.8 Hz, 2-OCH CH ), 55.72 (d, J = 152.1 Hz,
CP 2 3 CP
CH), 55.61 (CH ), 63.53 (2-OCH CH ), 114.26–114.45, 118.72,
1
3
2
3
6 4 6 5
29.29–129.53 (C H , C H ).
6
5
6
4
3
C NMR (CDCl , TMS): d = 16.22 (d, J = 5.8 Hz, 2-OCH CH ),
3
CP
2
3
+
MS (70 eV): m/z = 349 [M ], 212 [M – P(O)(OEt) ].
3
1
2
16.41 (d, J = 5.8 Hz, 2-OCH CH ), 56.00 (d, J = 150.6 Hz,
CH), 63.34 (d, J = 7.0 Hz, 2-OCH CH ), 63.50 (d, J = 7.0 Hz,
2
1
CP
2
3
CP
2
2
Anal. Calcd for C H NO P: C, 61.89; H, 6.88. Found: C, 61.85; H,
6
CP
2
3
CP
18
24
4
-OCH CH ), 112.60, 118.45, 120.04, 127.63–129.20, 135.30–
.84.
2 3
35.35, 142.26–142.49 (C H , C H ).
6
5
6
4
Compound g
IR: 3299 (NH) cm .
+
MS (70 eV): m/z = 353 [M ], 355 [M + 2], 216 [M – P(O)(OEt) ].
2
–
1
Anal. Calcd for C H ClNO P: C, 57.79; H, 5.95. Found: C, 57.75;
1
7
21
3
1
2
H NMR (CDCl , TMS): d = 1.09 (t, J = 7.1 Hz, 3 H, 2-
3
HH
H, 5.93.
2
OCH CH ), 1.21 (t, J = 7.1 Hz, 3 H, 2-OCH CH ), 3.69–4.09 (m,
2
3
HH
2
3
1
4
H, 2-OCH CH ), 4.66 (d, J = 23.7 Hz, 1 H, CH), 6.48 (d,
2 3 PH
Compound k
IR: 3297 (NH) cm .
2
2
JHH = 7.8 Hz, 2 H, C H , C H ), 6.63 (t, J = 7.3 Hz, 1 H, C H ,
–1
6
4
6
5
HH
6
4
2
2
C H ), 7.03 (t, J = 7.8 Hz, 2 H, C H , C H ), 7.23 (d, J = 8.4
6
5
HH
6
4
6
5
HH
1
H NMR (CDCl , TMS): d = 1.26–1.33 (m, 6 H, 2-OCH CH ),
.10–4.23 (m, 4 H, 2-OCH CH ), 4.47 (dd, J = 6.0 Hz, J
27.5 Hz, 1 H, CH), 6.23–6.30 (m, 1 H, CH=CH), 6.68–6.77 (m, 4
H, C H , CH=CH), 7.14–7.37 (m, 7 H, C H ).
3
2
1
3
Hz, 2 H, C H , C H ), 7.32–7.36 (m, 2 H, C H , C H ).
6
4
6
5
6
4
6
5
2
4
=
2
3
HH
PH
1
3
3
C NMR (CDCl , TMS): d = 16.64 (d, J = 5.8 Hz, 2-OCH CH ),
3
CP
2
3
3
1
1
6.83 (d, J = 5.8 Hz, 2-OCH CH ), 55.92 (d, J = 150.5 Hz,
CP 2 3 CP
6
5
6
5
CH), 63.68–63.88 (2-OCH CH ), 114.23, 119.06, 129.17–129.63,
2
3
13
C NMR (CDCl , TMS): d = 22.93–23.07 (2-OCH CH ), 60.53 (d,
3
2
3
1
34.14, 134.96, 146.29–146.52 (C H , C H ).
6 5 6 4
1J = 153.3 Hz, CH), 69.52 (d, J = 7.0 Hz, 2-OCH CH ), 69.96
2
CP
2
CP
2
3
+
MS (70 eV): m/z = 353 [M ], 355 [M + 2], 216 [M – P(O)(OEt) ].
2
(d, J = 7.0 Hz, 2-OCH CH ), 120.30, 124.90–139.56 (C H ).
CP 2 3 6 5
Synthesis 2004, No. 16, 2692–2696 © Thieme Stuttgart · New York