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Method B: A solution of PhPO2H2 (1 mmol), the corresponding ace-
tate 6 (or 7) (1.05 mmol), and Hunig’s base (4.0 mmol) in MeCN
(2 mL) in a Schlenk flask was degassed by applying three freeze–
pump–thaw cycles. The mixture is cooled to ꢀ788C and purged
with Ar for 15 min. Then, the mixture was precooled at ꢀ788C and
freshly distilled TMSCl (4.0 mmol) was added to the reaction vessel
at once. The temperature was slowly raised to 258C and the clear
solution was stirred for 6 h at room temperature. A workup was
performed as in Method A.
127.1, 127.2, 127.8, 128.0, 128.1, 128.2, 128.4, 128.9, 129.0, 129.2,
129.8, 129.9, 129.9, 131.5, 131.7, 131.9, 132.0, 132.3, 134.2, 134.3,
135.6, 135.7, 141.8, 142.0, 165.9, 166.2 ppm; 31P NMR (81 MHz,
CDCl3): d=42.4 ppm; IR (neat): n˜ =2980, 1712, 1438, 1237, 1127,
959, 720 cmꢀ1; ES-MS: m/z calcd for [C18H19O4P+H]+ 331.1; found:
331.1; HRMS: m/z calcd for C18H20O4P: 331.1099 [M+H]+; found:
331.1111.
Compound 14a: Prepared by method B. The major (E isomer) was
isolated as a white crystalline solid after recrystallization with
AcOEt. M.p. 130–1338C; TLC Rf(CHCl3/MeOH/AcOH 7:0.5:0.5)=0.44;
1H NMR (200 MHz, [D6]DMSO+2%TFA, major isomer): d=0.73 (d,
J=6.6 Hz, 6H; CH(CH3)2), 1.54 (sept, J=6.6 Hz, 1H; CHMe2), 2.07
(dt, J=3.9, 7.2 Hz, 2H; CH2CHMe2), 2.90 (d, 2J (P,H)=16.9 Hz, 2H;
PCH2), 6.20 (dt, J=4.7, 7.7 Hz, 1H; C=CH), 7.40–7.85 ppm (m, 5H;
aryl); 13C NMR (50 MHz, [D6]DMSO+2%TFA, major isomer): d=
Compound 9a: Prepared by method A. Viscous gum: TLC
Rf(CHCl3/MeOH/AcOH 7:0.5:0.5)=0.44; 1H NMR (200 MHz, CDCl3):
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d=1.10 (t, J=7.2 Hz, 3H; OCH2CH3), 3.03 (d, J (P,H)=18.7 Hz, 2H;
PCH2), 3.93 (q, J=7.2 Hz, 2H; OCH2CH3), 5.70 (d, J=5.2 Hz, 1H; C=
CHH), 6.22 (dd, J=0.7, 5.2 Hz, 1H; C=CHH), 7.30–7.77 ppm (m, 5H;
aryl); 13C NMR (50 MHz, CDCl3): d=13.9, 33.3 (d, 1J (P,C)=95 Hz),
60.9, 127.9, 128.2, 129.0, 129.1, 131.1 (d, 1J (P,C)=135 Hz), 131.1,
131.3, 131.4, 131.6, 131.9, 132.0, 165.8, 165.8 ppm; 31P NMR
(81 MHz, CDCl3): d=40.0 ppm; IR (neat): n˜ =2986, 1715, 1628,
1180, 1108, 961, 699 cmꢀ1; ES-MS: m/z calcd for [C12H15O4P+H]+:
255.1; found: 255.1; HRMS: m/z calcd for C12H16O4P: 255.0786 [M+
H]+; found: 255.0788.
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22.0, 27.8, 27.9, 35.5 (d, J (P,C)=94 Hz), 106.3, 106.5, 117.4, 117.5,
128.4, 128.6, 131.4, 131.5, 131.6, 132.1, 134.0, 151.1, 151.3 ppm;
31P NMR (81 MHz, [D6]DMSO, mixture of isomers): d=31.5 (minor),
32.6 ppm; IR (KBr): n˜ =2967, 2933, 2221, 1760, 1485, 1143, 1124,
969, 841, 753, 697 cmꢀ1; ES-MS m/z: calcd for [C14H18NO2PꢀH]ꢀ:
262.1; found: 262.2; HRMS: m/z calcd for C14H19NO2P: 264.1153
[M+H]+; found: 264.1159.
Compound 9b: Prepared by method B. Viscous gum: TLC
Rf(CHCl3/MeOH/AcOH 7:0.5:0.5)=0.35; 1H NMR (200 MHz, CDCl3):
d=1.02 (t, J=7.2 Hz, 3H; OCH2CH3), 1.63 (dd, J=4.8, 7.1 Hz, 3H;
Compound 14c: Prepared by method B. The major (E isomer) was
isolated as a white crystalline solid after recrystallization with
AcOEt. M.p. 183–1868C. TLC Rf(CHCl3/MeOH/AcOH 7:0.5:0.5)=0.14;
1H NMR (200 MHz, [D6]DMSO): d=3.07 (d, 2JPH =17.5 Hz, 2H;
PCH2), 7.06 (d, J=4.7 Hz, 1H; C=CH), 7.33–7.83 ppm (m, 10H; aryl);
13C NMR (50 MHz, [D6]DMSO): d=36.5, 102.6, 102.8, 118.4, 118.5,
128.2, 128.3, 128.5, 128.9, 130.2, 131.2, 131.4, 132.0, 132.0, 132.9 (d,
1J (P,C)=129 Hz), 133.5, 133.6, 134.2, 146.8, 147.0 ppm; 31P NMR
(81 MHz, [D6]DMSO): d=31.5 (minor), 32.9 ppm; IR (KBr): n˜ =3057,
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C=CHCH3), 3.00 (d, J (P,H)=18.9 Hz, 2H; PCH2), 3.81 (q, J=7.2 Hz,
2H; OCH2CH3), 6.88 (dt, J=7.0, 14.2 Hz, 1H; C=CH), 7.20–7.71 ppm
(m, 5H; aryl); 13C NMR (50 MHz, CDCl3): d=13.8, 14.7, 29.5 (d, 1J
(P,C)=96 Hz), 60.4, 123.8, 124.0, 127.7, 128.0, 131.2, 131.4, 131.5 (d,
1J (P,C)=133 Hz), 131.7, 131.7, 141.0, 141.1, 166.3 ppm; 31P NMR
(81 MHz, CDCl3): d=40.9 (minor), 41.3 ppm; IR (neat): n˜ =2980,
1711, 1647, 1276, 1174, 1126, 964, 733, 695 cmꢀ1; ES-MS: m/z calcd
for [C13H17O4P+H]+: 269.1; found: 269.1; HRMS: m/z calcd for
C13H18O4P: 269.0943 [M+H]+; found: 269.0938.
3026, 2973, 2214, 1619, 1439, 1236, 1137, 970, 826, 749, 699 cmꢀ1
;
ES-MS m/z calcd for [C16H14NO2PꢀH]ꢀ 282.1; found: 282.2; HRMS:
m/z calcd for C16H15NO2P: 284.0840 [M+H]+; found: 284.0838.
Compound 9e: Prepared by method B. Viscous gum: TLC Rf(CHCl3/
MeOH/AcOH 7:0.5:0.5)=0.64; 1H NMR (200 MHz, CDCl3): d=1.15
(t, J=7.1 Hz, 3H; OCH2CH3), 3.28 (d, 2J (P,H)=19.0 Hz, 2H; PCH2),
3.96 (q, J=7.1 Hz, 2H; OCH2CH3), 7.16–7.33 ppm (m, 11H; aryl,
Compound 9m: Prepared by method A. Viscous gum: TLC
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Rf(CHCl3/MeOH/AcOH 7:0.5:0.5)=0.34; H NMR (200 MHz, CD3OD):
d=2.19–2.42 (m, 2H; CH2CH2Ph), 2.43–2.69 (m, 2H; CH2Ph), 2.94 (d,
2J (P,H)=18.2 Hz, 2H; PCH2), 4.29–4.44 (m, 2H; COOCH2), 5.85–6.10
(m, 1H; CH=CHPh), 6.43 (d, J=15.6 Hz, 1H; CHPh), 6.70–6.90 (m,
1H; C=CH), 6.93–7.70 ppm (m, 15H; aryl); 13C NMR (50 MHz,
CDCl3): d=30.9, 33.3 (d, 1J (P,C)=95 Hz), 34.3, 65.3, 123.2, 125.9,
126.5, 127.9, 128.3, 128.3, 128.5, 131.3, 131.5, 131.9, 133.6, 136.1,
140.9, 145.6, 145.8, 166.1 ppm; 31P NMR (81 MHz, CDCl3): d=
41.7 ppm; IR (neat): n˜ =3053, 2927, 1713, 1495, 1438, 1266, 1225,
1154, 965, 735, 695 cmꢀ1; ES-MS m/z: calcd for [C27H27O4PꢀH]ꢀ
445.2; found: 445.3; HRMS: m/z calcd for C27H27NaO4P: 469.1544
[M+Na]+; found: 469.1552.
1
vinyl); 13C NMR (50 MHz, CDCl3): d=13.9, 30.9 (d, J (P,C)=97 Hz),
61.0, 123.7, 123.9, 127.8, 128.1, 128.3, 128.6, 129.2, 129.2, 131.2,
1
131.4, 131.8, 131.8, 131.9 (d, J (P,C)=133 Hz), 134.6, 134.6, 141.5,
141.7, 167.4, 167.4 ppm; 31P NMR (81 MHz, CD3OD): d=40.5
(minor), 41.1 ppm; IR (neat): n˜ =3057, 2980, 1710, 1268, 1202, 1155,
964, 736, 695 cmꢀ1; ES-MS: m/z calcd for [C18H19O4P+H]+: 331.1;
found: 331.1; HRMS: m/z calcd for C18H20O4P: 331.1099 [M+H]+;
found: 331.1114.
Compound 9 f: Prepared by method A. Viscous gum: TLC Rf(CHCl3/
MeOH/AcOH 7:0.5:0.5)=0.39; 1H NMR (200 MHz, CDCl3): d=1.14
(t, J=7.1 Hz, 3H; OCH2CH3), 1.27 (dd, J=7.4, 16.5 Hz, 3H; PCHCH3),
3.47 (dq, J=7.3, 17.6 Hz, 1H; PCH), 3.96 (dq, J=2.1, 7.1 Hz, 2H;
OCH2CH3), 5.71 (d, J=5.6 Hz, 1H; C=CHH), 6.28 ppm (d, J=5.6 Hz,
1H; C=CHH), 7.24–7.75 ppm (m, 5H; aryl); 13C NMR (50 MHz,
CDCl3): d=13.5, 13.6, 13.9, 34.8 (d, 1J (P,C)=96 Hz), 60.9, 127.0,
127.2, 127.8, 128.0, 129.3, 131.8, 131.8, 131.9, 132.0, 137.8, 137.9,
166.1, 166.2 ppm; 31P NMR (81 MHz, CDCl3): d=44.6 ppm; IR
(neat): n˜ =3056, 2980, 1717, 1438, 1262, 1141, 962, 696 cmꢀ1; ES-
MS m/z: calcd for [C13H17O4P + H]+ 269.1; found: 269.0; HRMS: m/
z calcd for C13H18O4P: 269.0943 [M+H]+; found: 269.0938.
Compound 9n: Prepared by method A. Viscous gum (Z/E=87:13):
TLC Rf(CHCl3/MeOH/AcOH 7:0.5:0.5)=0.26; 1H NMR (200 MHz,
CDCl3): d=1.04 (t, J=7.1 Hz; OCH2CH3), 1.43 (s, 9H; (CH3)3C), 2.34
(ddd, J=4.2, 6.7, 13.8 Hz, 2H; CHCH2), 3.06 (d, 2J (P,H)=19.0 Hz,
2H; PCH2); 3.20 (t, J=6.7 Hz, 2H; CH2NH), 3.82 (q, J=7.1 Hz, 2H;
OCH2CH3), 6.74 (dt, J=5.8, 7.3 Hz, 1H; C=CH), 7.29–7.79 ppm (m,
5H; aryl); 13C NMR (50 MHz, CDCl3): d=13.9, 28.4, 29.5, 29.9 (d,
1
1JPC =95 Hz), 39.3, 60.8, 79.0, 124.5, 124.7, 128.0, 128.2, 131.3 (d, J
(P,C)=133 Hz), 131.4, 131.6, 132.1, 132.1, 143.1, 143.3, 156.1, 166.1,
166.1 ppm; 31P NMR (81 MHz, CDCl3): d=40.4 (minor), 40.7 ppm;
IR (neat): n˜ =2976, 1709, 1523, 1272, 1172, 1051, 962, 731,
696 cmꢀ1; ES-MS: m/z calcd for [C19H28NO6PꢀH]ꢀ 396.2; found:
396.4; HRMS: m/z calcd for C19H29NO6P: 398.1733 [M+H]+; found:
398.1748.
Compound 9i: Prepared by method A. Viscous gum: TLC Rf(CHCl3/
MeOH/AcOH 7:0.5:0.5)=0.48; 1H NMR (200 MHz, CDCl3): d=1.17
(t, J=7.2 Hz, 3H; OCH2CH3), 4.05 (dq, J=2.2, 7.2 Hz, 2H; OCH2CH3),
2
4.58 (d, J (P,H)=17.0 Hz, 1H; PCH), 6.36 (d, J=5.5 Hz, 1H; C=CHH),
6.37 (d, J=5.5 Hz, 1H; C=CHH), 7.05–7.74 ppm (m, 10H; aryl);
13C NMR (50 MHz, CDCl3): d=14.0, 47.4 (d, 1J (P,C)=96 Hz), 61.2,
Compound 9o: Prepared by method A. Viscous gum: TLC
Rf(CHCl3/MeOH/AcOH 7:0.5:0.5)=0.29; 1H NMR (200 MHz, CDCl3):
Chem. Eur. J. 2015, 21, 3278 – 3289
3287
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