W. Dabkowski, J. Michalski et al.
18.63, 19.80, 26.42, 27.97, 37.83, 44.88, 47.36, 49.49 (d, J=6.0 Hz), 81.00
(d, J=6.7 Hz), 128.32 (d, J=12.7 Hz), 131.05 (d, J=10.0 Hz), 131.96,
132.68 ppm (d, J=128.2 Hz); 31P NMR (CDCl3): d=41.56 ppm; MS (CI):
m/z: 293 [M+H]+.
5.55 (m, 2H), 5.48–4.84 (m, 4H), 4.54–4.40 (m, 1H), 4.30–4.13 (m, 1H),
2.76 (dd, J=18.28, 69 Hz, 1H), 2.67 ppm (dd, J=18.03, 7.46 Hz);
13C NMR (CDCl3) d=133.9 (d, J=7 Hz), 133.3 (d, J=3 Hz), 132.7 (d,
J=10 Hz), 130.9 (d, J=125 Hz), 129.4 (d, J=13 Hz), 127.9 (d, J=9 Hz),
121.4 (d, J=13 Hz), 118.6, 65.9 (d, J=6 Hz), 36.9 ppm (d, J=97 Hz, 1 H);
31P NMR (CDCl3): d=41.5 ppm; 31P NMR and 13C NMR data were con-
sistent with those previously reported.[15d]
Benzyl diphenylphosphine oxide[31] (Table 1, entry 11): 1H NMR
(200.13 MHz, CDCl3): d=7.75–7.58 (m, 4H), 7.57–7.24 (m, 6H), 7.21–
7.07 (m, 5H), 3.65 ppm (d, 2H, J=13.75 Hz); 13C NMR (CDCl3): d=37.9
(d, J=66 Hz), 126.5 (d, J=3 Hz), 128.3 (d, J=12 Hz), 129.9 (d, J=5 Hz),
130.9 (d, J=9 Hz), 131.5 (d, J=3 Hz), 133.0 ppm; 31P NMR (CDCl3): d=
29.6 ppm; MS (FAB): m/z: 293.3 [M+1]+.
O-(1S)-Bornyl-(R)P-methylACHTNUTRGNE(NUG phenyl)phosphinate (more rapidly eluting
diastereoisomer): [a]D25 =+17.0 (c=1.01, CH2Cl2); 1H NMR (CDCl3): d=
7.73–7.54 (m, 2H), 7.45–7.26 (m, 3H), 4.46–4.36 (m, 1H), 1.97–1.77 (m,
2H), 1.68–1.36 (m, 2H), 1.54 (d, J=14.4 Hz), 1.25–1.04 (m, 2H), 0.98–
0.83 (m, 1H), 0.83 (s, 3H), 0.73 (s, 3H), 0.66 ppm (s, 3H); 13C NMR
(50.28 MHz, CDCl3): d=12.99, 15.79 (d, J=102.9 Hz), 18.47, 19.68, 26.30,
27.81, 36.76, 44.61, 47.17, 49.38 (d, J=4.6 Hz), 81.52 (d, J=6.7 Hz),
128.17 (d, J=12.7 Hz), 130.81 (d, J=10.1 Hz), 131.69, 132.72 ppm (d, J=
128.2 Hz); 31P NMR (CDCl3): d=41.10 ppm; MS (CI): m/z: 293 [M+H]+
.
Benzyl
N,N-diethyl
P(4-methoxybenzyl)phosphoamidite
(Table 1,
O-Bornyl-O-methyl methylphosphonate (Table 1, entry 2): 1H NMR
(200.13 MHz, CDCl3): d=4.56–4.47 (m, 1H), 3.64 (dd, J=11.01, 3.7 Hz,
3H), 2.29–2.09 (m, 1H), 1.94–1.22 (m, 3H), 1.16 (d, J=9.32 Hz, 3H),
1.12–0.81 (m, 3H), 0.79 ppm (s, 9H); 13C NMR (CDCl3): d=10.2 (d, J=
146 Hz), 12.6, 18.1, 19.3, 25.8, 27.4, 36.7, 44.3, 46.9, 48.8 (d, J=6 Hz), 51.0
(d, J=7 Hz), 81.1 ppm (d, J=8 Hz); 31P NMR (CDCl3): d=31.2,
31.6 ppm (1:1); MS (CI): m/z: 247 [M+H]+.
entry 12): H NMR (200.13 MHz, CD3OD): d=7.35–7.24 (m, 5H), 7.21
(dd, J=2, 8.5 Hz, 2H), 6.81 (d, J=8 Hz, 2H), 5.01 (dd, J=12.4, 12.0 Hz,
1H), 4.81 (dd, J=12.4, 12.0 Hz, 1H), 3.73 (s, 1H, 3.73), 3.13 (dd, J=
20.6 Hz, 1H), 3.03 (dd, J=20.6 Hz, 1H), 3.02 (m, 2H), 2.93 (m, 2H),
0.92 ppm (t, J=7 Hz, 2H); 13C NMR (CDCl3): d=13.9, 33.3 (d, J=
125.9 Hz), 38.5, 54.9, 64.6 (d, J=5.9 Hz), 113.6 (d, J=2.5 Hz), 123.8 (d,
J=8.2 Hz), 127.2, 128.1, 127.7, 130.6 (d, J=6.7 Hz), 136.6 (d, J=7.5 Hz),
158.1 ppm; 31P NMR (CD3OD): d=32.0 ppm; MS (CI): m/z: 348.2
[M+H]+.
O-Menthyl methylACHTUNGTRENNUNG
(phenyl)phosphinate[27] (Table 1, entry 3): 1H NMR
(200.13 MHz, CDCl3): d=7.86–7.73 (m, 4H), 7.56–7.26 (m, 6H), 4.34–
4.17 (m, 2H), 2.37–2.07 (m, 6H), 1.97–1.76 (m, 4H), 1.67 (d, J=14.45 Hz,
3H), 1.62 (d, J=14.30 Hz, 3H), 1.06–0.68 ppm (m, 18H); 13C NMR
(CDCl3): d=15.6, 20.0, 20.8, 21.7, 22.7, 25.6, 31.3, 33.9, 43.3, 48.5, 76.0,
128.2 (d, J=13 Hz), 130.6 (d, J=10 Hz), 131.7 (d, J=3 Hz), 133.8 ppm
(d, J=129 Hz); 31P NMR (CDCl3): d=40.0, 40.6 ppm; MS (CI): m/z: 295
[M+H]+.
N,N-Diethyl-P-methyl-P-phenyl phosphinamide (Table 1, entry 13):
1H NMR (200.13 MHz, CDCl3): d=7.73–7.58 (m, 2H), 7.44–7.26 (m,
3H), 3.11–2.83 (m, 4H), 1.61 (d, J=13.59 Hz, 3H), 1.02 ppm (t, J=
7.06 Hz, 6H); 13C NMR (CDCl3): d=14.8 (d, J=91 Hz), 13.9 (d, J=
7 Hz), 39.0 (d, J=4 Hz), 127.9 (d, J=12 Hz), 130.7 (d, J=10 Hz), 130.9
(d, J=3 Hz), 133.4 ppm (d, J=126 Hz); 31P NMR (CDCl3): d=35.7 ppm;
MS (CI): m/z: 212 [M+H]+.
O-Menthyl ethylACHTUNGTRENNUNG
(methyl)phosphinate[28] (Table 1, entry 4): 1H NMR
(200.13 MHz, CDCl3): d=4.20–4.03 (m, 1H), 2.17–1.93 (m, 2H), 1.77–
1.58 (m, 4H), 1.47–1.17 (m, 5H), 1.16–0.94 (m, 6H), 0.89–0.65 ppm (m,
9H); 13C NMR (CDCl3): d=5.5 (d, J=5 Hz), 12.8 (d, J=91 Hz), 15.0,
20.3, 21.2, 22.1, 23.3 (d, J=95 Hz), 24.8 (d, J=4 Hz), 30.7, 33.4, 42.9 (d,
J=7 Hz), 47.8 (d, J=6 Hz), 74.8 ppm (d, J=8 Hz); 31P NMR (CDCl3):
d=54.9, 55.5 ppm (1:2); MS (CI): m/z: 247 [M+H]+.
N-Ethyl-(1S)-N-(1-phenylethyl) (RP,SP) P-methyl P-phenyl phosphina-
mide (Table 1, entry 14): 1H NMR (200.13 MHz, CDCl3): d=7.89–7.77
(m, 4H), 7.51–7.45 (m, 8H), 7.36–7.20 (m, 8H), 4.84–4.60 (m, 2H), 3.09–
2.84 (m, 4H), 1.79 (d, J=13.53 Hz, 3H), 1.74 (d, J=13.48 Hz, 3H), 1.63
(d, J=7.02 Hz, 3H), 1.49 (d, J=7.03 Hz, 3H), 1.25–0.79 ppm (m, 6H);
13C NMR (CDCl3): d=14.9 (d, J=92 Hz), 15.1 (d, J=92 Hz), 16.2, 16.9,
18.0, 18.5, 36.5, 52.5 (d, J=4 Hz), 53.0 (d, J=3 Hz), 126.4, 126.5, 127.1 (d,
J=9 Hz), 127.5, 127.8 (d, J=13 Hz), 130.6 (d, J=10 Hz), 130.9, 133.4 (d,
J=125 Hz), 133.5 (d, J=125 Hz), 141.2 (d, J=7 Hz), 141.3 ppm (d, J=
4 Hz); 31P NMR (CDCl3): d=35.2, 35.8 ppm (1:1); MS (CI): m/z: 288
[M+H]+.
O-(2-Isopropyl-5-methylphenyl) ethylACHTNUTGRNEUNG(methyl) phosphinate (Table 1,
entry 5): 1H NMR (200.13 MHz, CDCl3): d=7.22 (s, 1H), 7.12 (d, J=
7.84 Hz, 1H), 6.89 (d, J=7.87 Hz, 1H), 3.23–3.10 (m, 1H), 2.27 (s, 3H),
2.00–1.82 (m, 2H), 1.55 (d, J=13.30 Hz, 3H), 1.31–1.14 ppm (m, 9H);
13C NMR (CDCl3): d=5.5 (d, J=5 Hz), 12.3 (d, J=90 Hz), 20.1, 22.4 (d,
J=96 Hz), 22.3, 26.0, 119.8, 124.7, 125.8, 135.1, 136.0, 147.7 ppm (d, J=
9 Hz); 31P NMR (CDCl3): d=55.6 ppm; MS (CI): m/z: 241 [M+H]+.
N-Ethyl-(1S)-N-(1-phenylethyl) P-methyl P-phenyl phosphinamide (rap-
idly eluting): [a]D =ꢀ54.4 (c=1.04 in CH2Cl2); 1H NMR (200.13 MHz,
CDCl3): d=7.90–7.79 (m, 2H), 7.51–7.44 (m, 5H), 7.49–7.08 (m, 3H),
4.84–4.68 (m, 1H), 3.12–2.71 (m, 2H), 1.79 (d, J=13.56 Hz, 3H), 1.49 (d,
J=7.02 Hz, 3H), 0.85 ppm (t, J=7.13 Hz, 3H); 13C NMR (CDCl3): d=
15.2 (d, J=93 Hz), 17.1, 18.2, 36.7 (d, J=4 Hz), 52.7 (d, J=4 Hz), 126.6,
127.3, 127.7, 128.0 (d, J=12 Hz), 130.8 (d, J=10 Hz), 131.1(d, J=3 Hz),
133.6 (d, J=125 Hz), 141.5 (d, J=4 Hz); 31P NMR (CDCl3): d=
35.3 ppm; MS (CI): m/z: 288 [M+H]+.
Methyl[di(1-naphthyl)]phosphine oxide (Table 1, entry 6): 1H NMR
(200.13 MHz, CDCl3): d=8.63–8.58 (m, 2H), 8.04–7.85 (m, 6H), 7.54–
7.40 (m, 6H), 2.32 ppm (d, J=12.98 Hz, 3H); 13C NMR (CDCl3): d=18.0
(d, J=75 Hz), 124.4, 126.3, 126.4, 127.2, 128.8, 129.4, 131.4, 132.9, 132.2,
133.7 ppm; 31P NMR (CDCl3): d=34.0 ppm; MS (CI): m/z: 317 [M+H]+.
Bis(4-methoxyphenyl)ACHTUNGTRENNUNG(methyl)phosphine oxide (Table 1, entry 7):
1H NMR (200.13 MHz, CDCl3): d=7.56–7.47 (m, 4H), 6.79 (d, J=
6.86 Hz, 4H), 3.77 (s, 6H), 1.97 ppm (d, J=13.25 Hz, 3H); 13C NMR
(CDCl3): d=16.4 (d, J=75 Hz), 55.2, 123.0 (d, J=112 Hz), 114.0 (d, J=
13 Hz), 132.5 (d, J=12 Hz), 162.3 ppm; 31P NMR (CDCl3): d=35.4 ppm;
MS (CI): m/z: 277 [M+H]+.
N-Ethyl-(1S)-N-(1-phenylethyl) P-methyl P-phenyl phosphinamide
(more slowly eluting): [a]D =ꢀ45.8 (c=1.03 in CH2Cl2); 1H NMR
(200.13 MHz, CDCl3): d=7.87–7.76 (m, 2H), 7.50–7.42 (m, 3H), 7.35–
7.19 (m, 5H), 4.75–4.15 (m, 1H), 3.06–2.88 (m, 2H), 1.74 (d, J=13.55 Hz,
3H), 1.62 (d, J=7.04 Hz, 3H), 0.81 ppm (t, J=7.10 Hz, 3H); 13C NMR
(CDCl3): d=15.6 (d, J=92 Hz), 17.0, 19.0, 37.0 (d, J=4 Hz), 53.4 (d, J=
4 Hz), 126.9, 127.4, 127.9, 128.2 (d, J=13 Hz), 131.0 (d, J=10 Hz),
131.3(d, J=3 Hz), 133.9 (d, J=125 Hz), 141.7 ppm (d, J=5 Hz); 31P NMR
(CDCl3): d=35.8 ppm; MS (CI): m/z: 288 [M+H]+.
Diethyl ethylphosphonate (Table 1, entry 8): 1H NMR (200.13 MHz,
CDCl3): d=3.90 (m, 4H), 1.61 (m, 2H), 1.13 (t, J=7.0 Hz, 6H),
0.93 ppm (dt, J=18.4, 7.7 Hz, 3H); 31P NMR (CDCl3); d=33.54 ppm;
1H NMR and 31P NMR date were consistent with those previously report-
ed.[29]
Allyl
diphenyl
phosphinoxide[30]
(Table 1,
entry 9):
1H NMR
4-Nitrobenzyl P-benzyl N,N-diethylphosphonamidate (Table 1, entry 15):
H NMR (200.13 MHz, CD3OD): d=8.12 (d, J=8.7 Hz, 2H), 7.39 (d, J=
8.6 Hz, 2H), 7.31–7.24 (m, 5H), 5.10 (dd, J=13.4, 13.4 Hz, 1H), 4.85 (dd,
J=13.4, 13.4 Hz, 1H), 3.22 (dd, J=20.6 Hz, 1H), 3.14 (dd, J=20.6 Hz,
1H), 3.06 (m, JP,H =6.9 Hz, 2H), 2.97 (m, JP, H =6.9 Hz, 2H), 0.94 ppm (t,
J=7.1 Hz, 2H); 13C NMR (CDCl3): d=13.9, 34.3 (d, J=125.9 Hz), 38.4
(d, J=4.8 Hz), 63.1 (d, J=6.06 Hz), 123.3, 126 (d, J=3.6 Hz), 127.3, 128.2
(d, J=2.4 Hz), 129 (d, J=6.0 Hz), 131 (d, J=8.4 Hz), 144.1 (d, J=
(200.13 MHz, CDCl3): d=7.76–7.63 (m, 4H), 7.47–7.03 (m, 6H), 5.83–
6.63 (m, 1H), 5.15–5.04 (m, 2H), 3.15–3.04 ppm (dd, J=14.5, 7.33 Hz,
2H); 13C NMR (CDCl3): d=35.9 (d, J=69 Hz), 120.8 (d, J=11 Hz),
126.8 (d, J=9 Hz), 128.4 (d, J=12 Hz), 130.8 (d, J=9 Hz), 131.7 (d, J=
3 Hz), 132.2 ppm (d, J=99 Hz); 31P NMR (CDCl3): d=29.9 ppm.
Allylphenylphosphinic acid allyl ester (Table 1, entry 10): 1H NMR
(200.13 MHz, CDCl3): d=7.77–7.59 (m, 2H), 7.51–7.33 (m, 3H), 5.95–
1754
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 1747 – 1756