C. Yuan et al.
HRMS (ESI): m/z: calcd for C20H36NO5PSNa: 456.1944 [M++23]; found:
456.1945.
(m, 18H); 13C NMR (100 MHz, CDCl3): d=149.84 (s), 128.25 (d, J=
10.5 Hz), 128.03 (d, J=11.9 Hz), 111.98 (d, J=6.7 Hz), 100.95 (d, J=
142.9 Hz), 61.23 (d, J=6.7 Hz), 57.89 (d, J=6.0 Hz), 57.53 (d, J=7.5 Hz),
55.54 (s), 54.62 (d, J=3.7 Hz), 40.17 (s), 33.03 (d, J=80.4 Hz), 22.27 (s),
19.61 (d, J=12.0 Hz), 16.19 (d, J=6.0 Hz), 15.16 (s), 15.00 ppm (s);
31P NMR (121 MHz, CDCl3): d=47.94 ppm (s); IR (KBr): n˜ =3213, 2979,
1616, 1524, 1476, 1363, 1222, 1185, 1116, 1070, 1037 cmÀ1; MS (ESI): m/z
(%): 499.2 [M+Na]+; HRMS (ESI): m/z: calcd for C22H41N2O5PSNa:
499.2366 [M++23]; found: 499.2361; elemental analysis (%) calcd for
C22H41N2O5PS: C 55.44, H 8.67, N 5.88; found: C 55.10, H 9.15, N 5.73.
Ethyl
1’,1’-diethoxyethyl-(SS,RC,SP)-(+)-2-(tert-butylsulfinylamino)-2-
(para-methylphenyl)ethylphosphinate (4b): Obtained as a colorless oil
(105 mg, 47%); [a]2D5 =+17.4 (c=1.02, CHCl3); 1H NMR (400 MHz,
CDCl3, Me4Si): d=7.29 (d, J=7.8 Hz, 2H), 7.13 (d, J=8.1 Hz, 2H), 5.30
(d, J=5.6 Hz, 1H), 4.83 (m, 1H), 4.02 (m, 2H), 3.63 (m, 4H), 2.42 (m,
2H), 2.29 (s, 3H), 1.43 (dd, J1 =15.2, J2 =4.5 Hz, 3H), 1.15 ppm (m,
18H); 13C NMR (100 MHz, CDCl3): d=138.14 (d, J=10.4 Hz), 137.80
(s), 129.29 (s), 127.58 (s), 101.06 (d, J=140.0 Hz), 61.81 (d, J=6.7 Hz),
58.03 (d, J=5.2 Hz), 57.80 (d, J=6.7 Hz), 56.09 (s), 54.70 (d, J=4.5 Hz),
33.00 (d, J=82.6 Hz), 22.44 (s), 21.08 (s), 20.27 (d, J=12.7 Hz), 16.43 (d,
J=5.2 Hz), 15.41 (s), 15.23 ppm (s); 31P NMR (121 MHz, CDCl3): d=
47.80 ppm (s); IR (KBr): n˜ =3226, 2980, 1516, 1457, 1390, 1225, 1185,
1155, 1038 cmÀ1; MS (ESI): m/z (%): 470.2 [M+Na]+; elemental analysis
(%) calcd for C21H38NO5PS: C 56.35, H 8.56, N 3.13; found: C 56.55, H
8.47, N 3.02.
Ethyl
1’,1’-diethoxyethyl-(SS,RC,RP)-(À)-2-(tert-butylsulfinylamino)-2-
(para-dimethylamino)ethylphosphinate 4d’: Obtained as a light-brown
solid (105 mg, 44%); m.p. 57–598C; [a]2D4 =À1.02 (c=0.93, CHCl3);
1H NMR (400 MHz, CDCl3, Me4Si): d=7.24 (d, J=8.1 Hz, 2H), 6.66 (d,
J=8.4 Hz, 2H), 5.12 (d, J=0.9 Hz, 1H), 4.64 (m, 1H), 4.05 (m, 2H), 3.61
(m, 4H), 2.88 (s, 6H), 2.59 (m, 1H), 1.96 (m, 1H), 1.43 (d, J=11.1 Hz,
3H), 1.13 ppm (m, 18H); 13C NMR (100 MHz, CDCl3): d=150.02 (s),
128.24 (s), 128.05 (s), 112.07 (s), 100.82 (d, J=138.5 Hz), 61.50 (d, J=
6.7 Hz), 57.73 (d, J=5.2 Hz), 57.50 (d, J=6.7 Hz), 55.64 (s), 54.08 (d, J=
4.5 Hz), 40.18 (s), 32.65 (d, J=81.9 Hz), 22.25 (s), 20.03 (d, J=12.7 Hz),
16.23 (d, J=5.2 Hz), 15.16 (s), 14.97 ppm (s); 31P NMR (121 MHz,
CDCl3): d=45.69 ppm (s); IR (KBr): n˜ =3215, 2978, 1616, 1525, 1362,
1223, 1186, 1167, 1038 cmÀ1; MS (ESI): m/z (%): 499.2 [M+Na]+; ele-
mental analysis (%) calcd for C22H41N2O5PS: C 55.44, H 8.67, N 5.88;
found: C 55.19, H 8.77, N 5.89.
Ethyl
1’,1’-diethoxyethyl-(SS,RC,RP)-(À)-2-(tert-butylsulfinylamino)-2-
(para-methylphenyl)ethylphosphinate (4b’): Obtained as a colorless oil
(96 mg, 43%); [a]2D5 =À5.65 (c=1.04, CHCl3); 1H NMR (400 MHz,
CDCl3, Me4Si): d=7.30 (d, J=8.0 Hz, 2H), 7.13 (d, J=8.0 Hz, 2H), 5.13
(d, J=2.8 Hz, 1H), 4.70 (d, J=4.0 Hz, 1H), 4.06 (m, 2H), 3.63 (m, 4H),
2.59 (m, 1H), 2.29 (s, 3H), 2.04 (m, 1H), 1.44 (d, J=8.7 Hz, 3H),
1.14 ppm (m, 18H); 13C NMR (100 MHz, CDCl3): d=138.18 (d, J=
10.4 Hz), 137.52 (s), 129.21 (s), 127.44 (s), 101.23 (d, J=142.9 Hz), 61.58
(d, J=7.5 Hz), 58.22 (d, J=5.2 Hz), 57.88 (d, J=6.7 Hz), 56.08 (s), 55.20
(d, J=4.4 Hz), 33.33 (d, J=80.4 Hz), 22.54 (s), 21.09 (s), 19.90 (d, J=
11.9 Hz), 16.40 (d, J=5.9 Hz), 15.46 (s), 15.31 ppm (s); 31P NMR
(121 MHz, CDCl3): d=47.81 ppm (s); IR (KBr): n˜ =3234, 2980, 1226,
1186, 1158, 1040 cmÀ1; MS (ESI): m/z (%): 470.1 [M+Na]+; elemental
analysis (%) calcd for C21H38NO5PS: C 56.35, H 8.56, N 3.13; found: C
56.58, H 8.59, N 3.23.
Ethyl
1’,1’-diethoxyethyl-(SS,RC,SP)-(+)-2-(tert-butylsulfinylamino)-2-
(para-methylsulfylphenyl)ethylphosphinate (4e): Obtained as a colorless
oil (110 mg, 46%); [a]2D5 =+23.4 (c=0.85, CHCl3); 1H NMR (400 MHz,
CDCl3, Me4Si): d=7.37 (d, J=8.1 Hz, 2H), 7.25 (d, J=8.7 Hz, 2H), 5.40
(d, J=4.5 Hz, 1H), 4.88 (m, 1H), 4.05 (m, 2H), 3.69 (m, 4H), 2.53 (s,
3H), 2.43 (m, 2H), 1.48 (d, J=11.1 Hz, 3H), 1.25 ppm (m, 18H);
13C NMR (100 MHz, CDCl3): d=138.04 (s), 137.97 (d, J=4.0 Hz), 127.96
(s), 126.55 (s), 101.16 (d, J=143.3 Hz), 61.60 (d, J=6.9 Hz), 58.18 (d, J=
5.6 Hz), 57.87 (d, J=6.8 Hz), 56.12 (s), 55.04 (d, J=4.4 Hz), 33.13 (d, J=
80.7 Hz), 22.50 (s), 19.82 (d, J=11.7 Hz), 16.35 (d, J=5.7 Hz), 15.71 (s),
15.41 (s), 15.27 ppm (s); 31P NMR (121 MHz, CDCl3): d=47.79 ppm (s);
IR (KBr): n˜ =3457, 3230, 2979, 1477, 1444, 1391, 1228, 1186, 1158,
1039 cmÀ1; MS (ESI): m/z (%): 502.1 [M+Na]+; HRMS (ESI): m/z: calcd
for C21H38NO5PS2Na: 502.1821 [M++23]; found: 502.1823.
Ethyl
1’,1’-diethoxyethyl-(SS,RC,SP)-(+)-2-(tert-butylsulfinylamino)-2-
(para-methoxylphenyl)ethylphosphinate (4c): Obtained as a colorless oil
(113 mg, 49%); [a]2D5 =+27.7 (c=0.75, CHCl3); 1H NMR (400 MHz,
CDCl3, Me4Si): d=7.30 (d, J=8.7 Hz, 2H), 6.83 (d, J=8.7 Hz, 2H), 5.26
(d, J=4.2 Hz, 1H), 4.81 (m, 1H), 4.00 (m, 2H), 3.73 (s, 3H), 3.62 (m,
4H), 2.38 (m, 2H), 1.42 (d, J=11.4 Hz, 3H), 1.14 ppm (m, 18H);
13C NMR (100 MHz, CDCl3): d=159.05 (s), 133.09 (d, J=9.7 Hz), 128.57
(d, J=8.2 Hz), 113.81 (d, J=11.9 Hz), 101.12 (d, J=142.9 Hz), 61.51 (d,
J=7.5 Hz), 58.11 (d, J=5.3 Hz), 57.78 (d, J=6.7 Hz), 55.92 (s), 55.11 (s),
54.81 (d, J=3.7 Hz), 33.18 (d, J=81.1 Hz), 22.44 (s), 19.77 (d, J=
12.7 Hz), 16.32 (d, J=6.0 Hz), 15.35 (s), 15.21 ppm (s); 31P NMR
(121 MHz, CDCl3): d=47.81 ppm (s); IR (KBr): n˜ =3217, 2979, 1614,
1517, 1390, 1249, 1183, 1078, 1031 cmÀ1; MS (ESI): m/z (%): 486.1
[M+Na]+; elemental analysis (%) calcd for C21H38NO6PS: C 54.41, H
8.26, N 3.02; found: C 54.28, H 8.36, N 3.03.
Ethyl
1’,1’-diethoxyethyl-(SS,RC,RP)-(À)-2-(tert-butylsulfinylamino)-2-
(para-methylsulfylphenyl)ethylphosphinate (4e’): Obtained as a white
solid (105 mg, 44%); m.p. 99—1008C; [a]2D2 =À9.18 (c=1.02, CHCl3);
1H NMR (400 MHz, CDCl3, Me4Si): d=7.33 (d, J=8.0 Hz, 2H), 7.20 (d,
J=8.4 Hz, 2H), 5.13 (d, J=2.0 Hz, 1H), 4.70 (m, 1H), 4.06 (m, 2H), 3.62
(m, 4H), 2.58 (m, 1H), 2.42 (s, 3H), 2.01 (td, J1 =4.4, J2 =13.8 Hz, 1H),
1.44 (d, J=12.0 Hz, 3H), 1.16 ppm (m, 18H); 13C NMR (100 MHz,
CDCl3): d=138.42 (s), 137.90 (d, J=9.7 Hz), 128.14 (s), 126.60 (s), 101.05
(d, J=140.0 Hz), 61.87 (d, J=6.7 Hz), 58.05 (d, J=5.2 Hz), 57.82 (d, J=
6.7 Hz), 56.14 (s), 54.56 (d, J=4.4 Hz), 32.83 (d, J=82.6 Hz), 22.43 (s),
20.26 (d, J=12.6 Hz), 16.44 (d, J=5.2 Hz), 15.65 (s), 15.42 (s), 15.23 ppm
(s); 31P NMR (121 MHz, CDCl3): d=47.64 ppm (s); IR (KBr): n˜ =3220,
3188, 2978, 1600, 1498, 1441, 1408, 1359, 1236, 1217, 1076, 1035 cmÀ1; MS
(ESI): m/z (%): 502.1 [M+Na]+; HRMS (ESI): m/z: calcd for
C21H38NO5PS2Na: 502.1821 [M++23]; found: 502.1820.
Ethyl
1’,1’-diethoxyethyl-(SS,RC,RP)-(À)-2-(tert-butylsulfinylamino)-2-
(para-methoxylphenyl)ethylphosphinate (4c’): Obtained as a white solid
(115 mg, 49%); m.p. 112–1138C; [a]2D4 =À3.47 (c=1.02, CHCl3);
1H NMR (400 MHz, CDCl3, Me4Si): d=7.38 (d, J=9.0 Hz, 2H), 6.90 (d,
J=9.0 Hz, 2H), 5.13 (d, J=2.7 Hz, 1H), 4.76 (m, 1H), 4.11 (m, 2H), 3.81
(s, 3H), 3.68 (m, 4H), 2.36 (m, 1H), 2.06 (m, 1H), 1.49 (d, J=11.7 Hz,
3H), 1.23 ppm (m, 18H); 13C NMR (100 MHz, CDCl3): d=159.38 (s),
133.12 (d, J=8.7 Hz), 128.93 (s), 113.99 (s), 101.12 (d, J=140.2 Hz), 61.88
(d, J=7.1 Hz), 58.10 (d, J=3.9 Hz), 57.87 (d, J=6.9 Hz), 56.08 (s), 55.25
(s), 54.37 (d, J=3.5 Hz), 32.90 (d, J=82.3 Hz), 22.52 (s), 20.33 (d, J=
12.1 Hz), 16.52 (d, J=5.1 Hz), 15.48 (s), 15.29 ppm (s); 31P NMR
(121 MHz, CDCl3): d=47.83 ppm (s); IR (KBr): n˜ =3217, 2978, 1614,
1517, 1250, 1183, 1078, 1030 cmÀ1; MS (ESI): m/z (%): 486.3 [M+Na]+;
elemental analysis (%) calcd for C21H38NO6PS: C 54.41, H 8.26, N 3.02;
found: C 54.31, H 8.16, N 2.95.
Ethyl
1’,1’-diethoxyethyl-(SS,RC,SP)-(+)-2-(tert-butylsulfinylamino)-2-
(para-fluorophenyl)ethylphosphinate (4 f): Obtained as a colorless oil
(106 mg, 47%); [a]2D4 =+17.2 (c=1.00, CHCl3); 1H NMR (400 MHz,
CDCl3, Me4Si): d=7.32 (m, 2H), 6.97 (t, J=8.8 Hz, 2H), 5.41 (d, J=
5.2 Hz, 1H), 4.85 (m, 1H), 3.97 (m, 2H), 3.89 (m, 1H), 3.63 (m, 3H),
2.36 (m, 2H), 1.42 (d, J=24.8 Hz, 3H), 1.18 ppm (m, 18H); 13C NMR
(100 MHz, CDCl3): d=162.11 (d, J=244.9 Hz), 136.96 (d, J=9.7 Hz),
129.09 (d, J=8.2 Hz), 115.19 (d, J=21.6 Hz), 101.07 (d, J=143.6 Hz),
61.52 (d, J=6.7 Hz), 58.11 (d, J=5.2 Hz), 57.81 (d, J=6.7 Hz), 56.06 (s),
54.85 (d, J=4.4 Hz), 33.13 (d, J=81.2 Hz), 22.42 (s), 19.71 (d, J=
11.9 Hz), 16.25 (d, J=5.1 Hz), 15.32 (s), 15.19 ppm (s); 19F NMR
(282 MHz, CHCl3): d=À110.41 ppm (s); 31P NMR (121 MHz, CDCl3):
d=47.72 ppm (s); IR (KBr): n˜ =3241, 2980, 1605, 1512, 1476, 1392, 1226,
1161, 1039 cmÀ1 (s); MS (ESI): m/z (%): 474.1 [M+Na]+; elemental anal-
Ethyl
1’,1’-diethoxyethyl-(SS,RC,SP)-(+)-2-(tert-butylsulfinylamino)-2-
(para-dimethylamino)ethylphosphinate (4d): Obtained as a light-yellow
oil (117 mg, 49%); [a]2D4 =+53.5 (c=1.05, CHCl3); 1H NMR (400 MHz,
CDCl3, Me4Si): d=7.27=(d, J=8.7 Hz, 2H), 6.69 (d, J=9.0 Hz, 2H),
5.20 (d, J=3.6 Hz, 1H), 4.79 (m, 1H), 4.09 (m, 2H), 3.67 (m, 4H), 2.92
(s, 6H), 2.51 (m, 1H), 2.33 (m, 1H), 1.46 (d, J=11.1 Hz, 3H), 1.20 ppm
4096
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 4088 – 4101