Catalyst–free synthesis of cycloalkenyl phosphonates · 2014-03-12 · 1 Supplementary Information for Catalyst–free synthesis of cycloalkenyl phosphonates Xunfu Xu,a Hu Chen,*ab

1

Supplementary Information for

Catalyst–free synthesis of cycloalkenyl phosphonates

Xunfu Xu,a Hu Chen,*ab Yulei Wang,a Yuxing Gao,a Guo Tang*a and Yufen Zhaoa

a College of Chemistry and Chemical Engineering and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen 361005, P. R. China. [email protected]; b Department of Chemistry and Chemical Engineering, Hefei Normal University, Hefei 230601, China. [email protected] Table of Contents Page 2 - 3 Analysis of byproduct 3aa Page 3 31P NMR spectra for the synthesis of 3k Page 4 – 12 Spectral Data

Page 13 – 31 1H NMR , 13C NMR and 31P NMR Spectra of all compounds

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2014

2

Analysis of byproduct 3aa

[M+Na] m/z : 393.0

3

301.6

371.5393.1

459.1

erhuanwuerxi-linque-D-A-0412.d: +MS

277.1

315.0

343.0

371.0

erhuanwuerxi-linque-D-A-0412-2.d: +MS2(371.4)

248.9 277.0

314.9

342.9

erhuanwuerxi -linque-D-A-0412-3.d: +MS3(371.4->343.0)

166.9

232.9

248.9

296.9

314.9

erhuanwuerxi-linque-D-A-0412-4.d: +MS4(371.4->343.0->314.9)

0

2

4

4x10Intens.

0

1

2

3

4x10

0

2000

4000

6000

8000

0

500

1000

1500

31P NMR spectra for the synthesis of 3k. The yield of the crude product 3k was determined by 31P NMR spectrum after reaction at 120 °C for 48 h. The conversion of alkynyl phosphonate was almost quantitative.

-70-60-50-40-30-20-1070 60 50 40 30 20 10 0 ppm

-0.50

14.91

1.13

98.87

4

Spectral Data

Diethyl 3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3a)

Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.61 – 7.49 (m, 2H), 7.43 – 7.23 (m, 3H), 6.96 (m, 2H), 4.14 –

4.05 (m, 1H), 4.05 – 3.72 (m, 5H), 2.27 (dt, J = 6.6, 1.4 Hz, 1H), 2.06 (dq, J = 6.6, 1.5 Hz, 1H), 1.17 (td,

7.0, 0.4 Hz, 3H), 1.12 (td, 7.2, 0.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 170.6 (d, JPC = 14.3 Hz),

143.5, 140.9 (d, JPC = 2.1 Hz), 135.6 (d, JPC = 3.5 Hz), 134.5 (d, JPC = 201.9 Hz), 128.7, 127.9, 127.5 (d,

JPC = 1.6 Hz), 71.4 (d, JPC = 6.2 Hz), 61.5 (d, JPC = 5.5 Hz), 61.3 (d, JPC = 5.4 Hz), 58.4 (d, JPC = 16.3 Hz),

55.2 (d, JPC = 12.2 Hz), 16.1 (d, JPC = 7.2 Hz), 16.0 (d, JPC = 7.3 Hz). 31P NMR (160 MHz, CDCl3) δ 17.6.

IR (film): 3062, 2982, 2937, 2905, 2869, 1591, 1557, 1492, 1445, 1391, 1293, 1245, 1162, 1095, 1052,

1025, 965, 795, 766, 724, 698, 661, 604, 577, 546, 508 cm-1. HRMS (ESI) calcd for C17H22NaO3P,

328.1204; found 328.1209.

Dimethyl 3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3b)

Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.61 – 7.44 (m, 2H), 7.35 (m, 3H), 7.04 – 6.86 (m, 2H), 4.17 –

4.02 (m, 1H), 3.95 (d, J = 1.4 Hz, 1H), 3.57 (d, J = 11.2 Hz, 3H), 3.47 (d, J = 11.4 Hz, 3H), 2.32 – 2.20

(m, 1H), 2.08-2.05 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 171.7 (d, JPC = 14.7 Hz), 143.5, 140.9 (d, JPC

= 2.3 Hz), 135.3(d, JPC = 3.8 Hz), 133.4(d, JPC = 201.6 Hz), 128.9, 128.0, 127.3 (d, JPC = 1.7 Hz), 71.4 (d,

JPC = 6.2 Hz), 58.5 (d, JPC = 16.4 Hz), 55.2 (d, JPC = 12.1 Hz), 52.1 (d, JPC = 5.5 Hz), 51.8 (d, JPC = 5.5

Hz). 31P NMR (160 MHz, CDCl3) δ 20.6. IR (film): 3062, 2988, 2950, 2849, 1590, 1492, 1447, 1293,

1247, 1183, 1052, 1028, 930, 825, 795, 767, 725, 698, 661, 602, 575, 545 cm-1. HRMS (ESI) calcd for

C15H17NaO3P, 299.0813; found 299.0800.

Diisopropyl (3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3c)

5

Brown oil; 1H NMR (400 MHz, CDCl3) δ 7.58 – 7.55 (m, 2H), 7.37– 7.27 (m, 3H), 6.96 (dd, J = 4.8, 3.1

Hz, 1H), 6.90 (dd, J = 4.8, 3.2 Hz, 1H), 4.58 – 4.45 (m, 5H), 4.09 (d, J = 1.2 Hz, 1H), 3.93 - 3.92(m, 1H),

2.24 - 2.22 (m, 1H), 2.04 - 2.01 (m, 1H), 1.26 (d, J = 6.2 Hz, 3H), 1.21 (d, J = 6.2 Hz, 3H), 1.11 (d, J =

6.2 Hz, 3H), 1.07 (d, J = 6.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 169.2 (d, JPC = 15.0 Hz), 143.5 (d,

JPC = 1.3 Hz), 140.6 (d, JPC = 2.0 Hz), 135.8 (d, JPC = 201.7 Hz), 135.7 (d, JPC = 3.8 Hz), 128.4, 127.8,

127.7 (d, JPC = 1.5 Hz), 71.2 (d, JPC = 6.0 Hz), 70.1 (d, JPC = 5.7 Hz), 70.0 (d, JPC = 5.5 Hz), 58.4 (d, JPC

= 16.3 Hz), 55.5 (d, JPC = 12.3 Hz), 24.0 (d, JPC = 4.0 Hz), 23.9 (d, JPC = 4.2 Hz), 23.7 (d, JPC = 4.9 Hz),

23.5 (d, JPC = 5.1 Hz). 31P NMR (160 MHz, CDCl3) δ 15.0. IR (film): 3060, 2978, 2935, 2871, 1721,

1657, 1594, 1492, 1466, 1448, 1385, 1374, 1242, 1177, 1141, 1105, 986, 896, 766, 722, 697, 660, 605,

579, 549 cm-1. HRMS (ESI) calcd for C19H25NaO3P, 355.1439; found 355.1440.

Dibutyl 3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3d)

Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.58 – 7.50 (m, 2H), 7.41 – 7.25 (m, 3H), 6.98 – 6.91 (m, 2H),

4.10 (s, 1H), 4.09-3.73 (m, 5H), 2.26 (dt, J = 6.6, 1.4 Hz, 1H), 2.10 – 1.98 (m, 1H), 1.56 – 1.35 (m, 4H),

1.35 – 1.16 (m, 4H), 0.85 (dt, J = 14.5, 7.4 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 170.5 (d, JPC = 14.4

Hz), 143.5, 140.9(d, JPC = 2.1 Hz), 135.6(d, JPC = 3.7 Hz), 134.5(d, JPC = 201.9 Hz), 128.6, 127.9, 127.5

(d, JPC = 1.6 Hz), 71.4 (d, JPC = 6.2 Hz), 65.2 (d, JPC = 5.8 Hz), 64.9 (d, JPC = 5.6 Hz), 58.4 (d, JPC = 16.2

Hz), 55.3 (d, JPC = 12.1 Hz), 32.3 (d, JPC = 6.8 Hz), 32.2 (d, JPC = 7.0 Hz), 18.7 (d, JPC = 6.6 Hz), 13.6 (d,

JPC = 3.2 Hz). 31P NMR (160 MHz, CDCl3) δ 17.7. IR (film): 3063, 2960, 2933, 2872, 1591, 1492, 1461,

1295, 1247, 1065, 1023, 980, 902, 765, 723, 697, 605, 579, 548 cm-1. HRMS (ESI) calcd for C21H30O3P,

361.1927; found 361.1925.

Diphenyl 3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphine oxide(3e)

6

White solid, m.p. 85-87 °C ; 1H NMR (400 MHz, CDCl3) δ 7.70 – 7.61 (m, 2H), 7.53 – 7.38 (m, 5H),

7.38 – 7.27 (m, 3H), 7.21 (m, 2H), 7.11 – 7.05 (m, 3H), 7.01 (dd, J = 4.9, 3.2 Hz, 1H), 6.73 (dd, J = 4.7,

3.0 Hz, 1H), 4.03 – 3.93 (m, 1H), 3.71 – 3.60 (m, 1H), 2.39 (dt, J = 6.6, 1.4 Hz, 1H), 2.02 (dd, J = 6.6, 1.1

Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 172.1 (d, J = 9.1 Hz), 143.1, 141.0(d, JPC = 2.1 Hz), 138.2(d, JPC

= 108.6 Hz), 135.5(d, JPC = 3.1Hz), 133.3(d, JPC = 108.9 Hz), 132.0 (d, JPC = 106.4 Hz), 131.4(d, JPC =

9.8 Hz),131.3 (d, JPC = 3.1 Hz), 131.2(d, JPC = 9.6 Hz), 131.1(d, JPC = 3.0 Hz), 128.4(d, JPC = 11.7Hz),

128.3, 128.0(d, JPC = 12.3 Hz), 127.6, 127.4 (d, JPC = 1.3 Hz), 71.3 (d, JPC = 5.1 Hz), 59.2 (d, JPC = 11.6

Hz), 55.8 (d, JPC = 11.9 Hz). 31P NMR (160 MHz, CDCl3) δ 22.8. IR (film): 3057, 2967, 2939, 2869,

1717, 1586, 1556, 1489, 1438, 1296, 1261, 1182, 1115, 1025, 927, 808, 754, 721, 698, 661, 591, 573, 545,

523 cm-1. HRMS (ESI) calcd for C25H21NaOP, 391.1222; found 391.1230.

Diethyl 3-o-tolylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3f)

Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.24 – 7.11 (m, 3H), 7.00 (dd, J = 5.1, 3.0 Hz, 2H), 6.88 (dd, J

= 4.9, 3.2 Hz, 1H), 4.07 (s, 1H), 3.94 – 3.68 (m, 5H), 2.38 (d, J = 6.5 Hz, 1H), 2.23 (s, 3H), 2.12 – 1.99

(m, 1H), 1.08 (dt, J = 19.3, 7.1 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 171.6 (d, JPC = 14.1 Hz), 143.6,

141.1 (d, JPC = 2.4 Hz), 137.2 (d, JPC = 3.5 Hz), 137.0(d, JPC = 204.0 Hz), 135.1 (d, JPC = 2.0

Hz),129.7,127.9,127.4,125.3, 72.6 (d, JPC = 6.0 Hz), 61.4 (d, JPC = 6.1 Hz), 61.3 (d, JPC = 6.8 Hz), 59.1 (d,

JPC = 16.5 Hz), 53.8 (d, JPC = 13.3 Hz), 20.2, 16.1 (d, JPC = 6.8 Hz), 16.0 (d, JPC = 7.0 Hz). 31P NMR (160

MHz, CDCl3) δ 17.1. IR (film): 3065, 2982, 2935, 2900, 2868, 1620, 1596, 1558, 1482, 1453, 1391,

1296, 1244, 1199, 1162, 1095, 1052, 1027, 964, 868, 795, 755, 728, 654, 609, 582, 560 cm-1. HRMS (ESI)

calcd for C18H23NaO3P, 341.1277; found 341.1276.

Diethyl (3-(p-tolyl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3g)

7

Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.43 (dd, J = 6.4, 1.7 Hz, 2H), 6.15 (d, J = 7.9 Hz, 2H), 6.93 –

6.87 (m, 2H),4.04 – 3.76 (m, 6H), 2.33 (s, 3H), 2.22 – 2.20 (m, 1H), 2.01 – 1.99 (m, 1H), 1.13 (dt, J =

21.8, 7.0 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 170.6 (d, JPC = 14.1 Hz), 143.4, 140.7 (d, JPC = 2.1 Hz),

138.7, 133.1 (d, JPC = 200.7 Hz), 132.5 (d, JPC = 3.8 Hz), 128.5, 127.4 (d, JPC = 1.4 Hz), 71.1 (d, JPC = 6.3

Hz), 61.3 (d, JPC = 5.2 Hz), 61.1 (d, JPC = 5.3 Hz), 58.3 (d, JPC = 16.5 Hz), 55.1 (d, JPC = 12.1 Hz), 21.2,

16.1 (d, JPC = 6.6 Hz), 16.0 (d, JPC = 7.2 Hz). 31P NMR (160 MHz, CDCl3) δ 17.1. IR (film): 2982, 2935,

1508, 1443, 1391, 1290, 1231, 1163, 1095, 1052, 1024, 967, 820, 603, 573, 537 cm-1. HRMS (ESI) calcd

for C18H23NaO3P, 341.1283; found 341.1278.

Diethyl 3-(4-fluorophenyl)bicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3h)


4.07 (d, J = 0.9 Hz, 1H), 4.03 – 3.69 (m, 5H), 2.25 (dd, J = 6.6, 1.4 Hz, 1H), 2.05 (dd, J = 6.6, 1.5 Hz,

1H), 1.25 – 1.18 (m, 3H), 1.17 – 1.09 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 169.5 (d, JPC = 14.2 Hz),

164.2, 161.7, 143.6 (d, JPC = 1.0 Hz),, 140.6 (d, JPC = 2.3 Hz), 133.4(d, JPC = 201.0 Hz), 131.6, 129.5 (d,

JPC = 1.7 Hz), 129.4 (d, JPC = 1.6 Hz), 114.9 (d, JPC = 21.6 Hz), 71.4 (d, JPC = 6.2 Hz), 61.5 (d, JPC = 5.4



1600, 1506, 1445, 1392, 1293, 1235, 1162, 1097, 1052, 1025, 966, 840, 794, 732, 603, 575, 539 cm-1.

HRMS (ESI) calcd for C17H20FNaO3P, 345.1026; found 345.1026.

Diethyl 3-(3-chlorophenyl)bicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3i)

8


6.95 (ddt, J = 8.0, 7.4, 3.8 Hz, 2H), 4.13 – 4.06 (m, 1H), 4.05 – 3.79 (m, 5H), 2.26 (dt, J = 6.7, 1.5 Hz,

1H), 2.06 (dt, J = 6.7, 1.5 Hz, 1H), 1.24 – 1.09 (m, 6H). 13C NMR (100 MHz, CDCl3) δ 168.8 (d, JPC =

13.9 Hz), 143.6, 140.8 (d, JPC = 2.3 Hz), 137.4 (d, JPC = 5.2 Hz), 136.5(d, JPC = 201.0 Hz), 133.8, 129.2,

128.5, 127.3 (d, JPC = 1.7 Hz), 125.9, 71.6 (d, JPC = 6.2 Hz), 61.6 (d, JPC = 5.7 Hz), 61.4 (d, JPC = 5.5 Hz),

58.4 (d, JPC = 16.0 Hz), 55.4 (d, JPC = 12.0 Hz), 16.2 (d, JPC = 4.7 Hz), 16.1 (d, JPC = 4.8 Hz). 31P NMR

(160 MHz, CDCl3) δ 16.7. IR (film): 3067, 2982, 2937, 2906, 2869, 1586, 1559, 1474, 1392, 1296, 1246,

1162, 1096, 1052, 1025, 965, 790, 713, 696, 611, 580 cm-1. HRMS (ESI) calcd for C17H20ClNaO3P,

361.0731; found 361.0739.

Diethyl (3-(4-bromophenyl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3j)

Brown oil; 1H NMR (400 MHz, CDCl3) δ 7.48 – 7.46 (m, 2H), 7.41 – 7.39 (m, 2H), 6.94 – 6.89(m, 2H),

4.06 – 3.76 (m, 6H), 2.23 (d, J = 6.6 , 1H), 2.03 (dd, J = 6.7, 1.3 Hz, 1H), 1.21 – 1.17 (m, 3H), 1.15 –

1.11 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 169.3 (d, JPC = 14.3 Hz), 143.5, 140.7 (d, JPC = 2.2 Hz),

135.5 (d, JPC = 200.2 Hz), 134.3 (d, JPC = 4.1 Hz), 131.0, 129.1 (d, JPC = 1.3 Hz), 122.8, 71.4 (d, JPC = 6.2


JPC = 7.1 Hz), 16.1 (d, JPC = 7.8 Hz). 31P NMR (160 MHz, CDCl3) δ 17.0. IR (film): 2981, 2934, 1584,

1485, 1443, 1394, 1287, 1244, 1163, 1024, 971, 827, 796, 730, 602, 577, 553 cm-1. HRMS (ESI) calcd

for C17H20BrNaO3P, 405.0231; found 405.0240.

Diethyl (3-(4-cyanophenyl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3k)

Deep yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.63 (s, 4H), 6.96 – 6.92 (m, 2H), 4.08 – 3.79 (m, 6H) ,

2.26 – 2.24 (m, 1H), 2.09 – 2.07 (m, 1H), 1.17 (dt, J = 32.9, 7.1 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ

178.3 (d, JPC = 13.9 Hz), 143.5 (d, JPC = 1.5 Hz), 140.7 (d, JPC = 2.2 Hz), 140.0 (d, JPC = 3.9 Hz), 138.9 (d,

JPC = 199.7 Hz), 131.6, 128.1 (d, JPC = 1.4 Hz), 118.7, 111.9, 71.7 (d, JPC = 6.1 Hz), 61.7 (d, JPC = 5.5


9


1290, 1246, 1163, 1095, 1054, 1025, 965, 842, 797, 719, 603, 573, 551, 518 cm-1. HRMS (ESI) calcd for

C18H20NNaO3P, 352.1078; found 352.1081.

Diethyl (3-(thiophen-2-yl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3l)

Pale yellow oil;1H NMR (400 MHz, CDCl3) δ 7.83 (d, J = 3.7 Hz, 1H), 7.39 (d, J = 4.6 Hz, 1H), 7.09 (dd,

J = 5.0, 3.8 Hz, 1H), 6.91 – 6.90 (m, 1H), 6.84 – 6.83 (m, 1H), 4.11 –3.86 (m, 6H), 2.20 (d, J = 6.7 Hz,

1H), 2.01 (dd, J = 6.7, 1.4 Hz, 1H), 1.25 (dt, J = 16.6, 7.1Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 162.2

(d, JPC = 14.1 Hz), 143.6, 139.8 (d, JPC = 2.0 Hz), 137.9 (d, JPC = 4.7 Hz), 130.3 (d, JPC = 201.9 Hz),

129.3, 128.2, 127.9,70.1 (d, JPC = 6.0 Hz), 61.5 (d, JPC = 5.0 Hz), 61.4 (d, JPC = 5.1Hz), 59.0 (d, JPC =

11.4 Hz), 55.8 (d, JPC = 11.4 Hz), 16.2 (d, JPC = 6.5 Hz), 16.2 (d, JPC = 6.7 Hz). 31P NMR (160 MHz,

CDCl3) δ 17.1. IR (film): 2963, 2934, 2870, 1729, 1616, 1452, 1384, 1374, 1260, 1177, 1105, 1018, 981,

799, 595 cm-1. HRMS (ESI) calcd for C15H19NaO3PS, 333.0690; found 333.0691.

Ethyl methyl 3-butylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3m)

Yellow oil;1H NMR (400 MHz, CDCl3) δ 6.81 (dd, J = 4.8, 3.1Hz, 1H), 6.69 (dd, J = 4.8, 3.1Hz 1H),

4.08 - 3.84 (m, 4H), 3.79 (s, 1H), 3.56 (s, 1H), 2.70 - 2.57 (m, 2H), 2.01 (d, J = 6.3 Hz, 1H), 1.93 (dd, J =

6.4, 1.2 Hz, 1H), 1.51 - 1.25 (m,10H), 0.91 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 177.0 (d,

JPC = 17.8 Hz), 143.3, 140.8, 132.4 (d, JPC = 202.5 Hz), 71.8 (d, JPC = 6.0 Hz), 61.0, 60.9, 56.0 (d, JPC =

17.7 Hz), 53.0 (d, JPC =13.1 Hz), 30.1 (d, JPC = 2.7 Hz), 29.2 (d, JPC = 2.1 Hz), 22.5, 16.3 (d, JPC = 5.7

Hz), 16.3 (d, JPC = 6.3Hz), 13.9. 31P NMR (160 MHz, CDCl3) δ 18.7. IR (film): 3070, 2980, 2936, 2903,

2868, 1573, 1556, 1477, 1443, 1419, 1390, 1364, 1298, 1276, 1246,1193, 1163, 1095, 1050, 1024, 961,

863, 847, 792, 720, 673, 635, 597, 579, 535, 506 cm-1. HRMS (ESI) calcd for C15H17NaO3P, 299.0808;

found 299.0800.

Diisopropyl (3-(3-chloropropyl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3n)

10

Yellow oil;1H NMR (400 MHz, CDCl3) δ 6.82 (dd, J = 5.0, 3.0Hz, 1H), 6.68 (dd, J = 4.9, 3.2Hz 1H),

4.66-4.43 (m, 2H), 3.76 (s, 1H), 3.53 (s, 1H), 3.51 – 3.43 (m, 2H), 2.88 – 2.80 (m, 1H), 2.78 – 2.70 (m,

1H), 2.00 – 1.82 (m, 4H), 1.33(d, J = 6.2Hz, 3H), 1.30 (d, J = 6.2Hz, 3H), 1.27 (d, J = 6.2Hz, 3H), 1.19 (d,

J = 6.2Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 173.0 (d, JPC = 17.4 Hz), 143.5, 140.4 (d, JPC = 2.1 Hz),

135.6 (d, JPC = 203.4 Hz), 71.9 (d, JPC = 5.9 Hz), 69.7, 69.6, 56.0 (d, JPC = 17.5 Hz), 53.1 (d, JPC =12.4

Hz), 44.3, 30.4 (d, JPC = 2.0 Hz), 27.9 (d, JPC = 2.7 Hz), 24.1 (d, JPC = 3.7 Hz), 24.1 (d, JPC = 3.5 Hz),

24.0 (d, JPC = 4.4 Hz), 23.9 (d, JPC = 4.4 Hz). 31P NMR (160 MHz, CDCl3) δ 15.2. IR (film): 3067, 2976,

2935, 2869, 1726, 1616, 1557, 1451, 1373, 1385, 1302, 1283, 1240, 1178, 1140, 1107, 1042, 979, 849,

882, 798, 772, 723, 649, 596, 523 cm-1. HRMS (ESI) calcd for C16H26ClNaO3P, 355.1206; found

355.1212.

Diethyl (3-(hydroxymethyl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3o)

Brown oil; 1H NMR (400 MHz, CDCl3) δ 6.81 (dd, J = 5.0,3.0Hz, 1H), 6.69 (dd, J = 4.9,3.3Hz 1H), 5.52

(s, 1H), 4.63 (dd, J = 17.8,3.5Hz 1H), 6.69 (dd, J = 17.8,4.0Hz 1H), 4.13 – 3.78 (m, 4H), 3.75 (s, 1H),

3.50 (s, 1H), 2.03 (d, J = 6.6 Hz, 1H), 1.91 (dd, J = 6.6,1.1 Hz, 1H), 1.31 (t, J = 7.1 Hz, 3H), 1.23 (t, J =

7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 177.5 (d, JPC = 18.2 Hz), 143.3, 140.5 (d, JPC = 2.3 Hz),

132.2 (d, JPC = 201.1 Hz), 71.6 (d, JPC = 5.8 Hz), 62.5 (d, JPC = 4.2 Hz), 61.8 (d, JPC = 5.1 Hz), 61.7 (d,

JPC =5.1 Hz), 55.5 (d, JPC = 16.6 Hz), 53.5 (d, JPC = 11.3 Hz), 16.2(d, JPC = 6.4 Hz), 16.1 (d, JPC = 6.7Hz). 31P NMR (160 MHz, CDCl3) δ 19.7. IR (film): 2983, 2938, 2870, 1725, 1669, 1392, 1281, 1226, 1164,

1095, 1024, 971, 796, 587 cm-1. HRMS (ESI) calcd for C12H19NaO4P, 281.0919; found 281.0925.

Diethyl (3-(thiophen-2-yl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3p)

11

Yellow oil;1H NMR (400 MHz, CDCl3) δ 9.95 (s, 1H), 7.36 -7.19 (m,5H), 6.89 (dd, J = 4.1, 4.1Hz, 1H),

6.879 (dd, J = 4.8, 3.2Hz, 1H), 4.71 - 4.63 (m, 1H), 4.55 - 4.45 (m, 2H), 4.44 - 4.34 (m, 2H), 3.93 (s, 1H),

2.06 (d, J = 6.8 Hz, 1H), 1.94 (d, J = 6.8Hz, 1H), 1.36 (d, J = 6.2Hz, 3H), 1.30 (d, J = 6.2Hz, 3H), 1.26 (d,

J = 6.2Hz, 3H), 1.11 (d, J = 6.2Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 164.2 (d, JPC = 15.4 Hz), 163.0 (d,

JPC = 4.6 Hz), 143.7 (d, JPC = 194.2 Hz), 142.6 (d, JPC = 2.4 Hz), 141.6 (d, JPC = 1.3 Hz), 138.9, 128.4,

127.9, 127.0, 71.5 (d, JPC = 6.9 Hz), 71.4 (d, JPC = 9.5 Hz), 56.3 (d, JPC = 9.3 Hz), 54.8 (d, JPC =15.8 Hz),

43.7, 24.0 (d, JPC = 3.8 Hz), 23.9 (d, JPC = 4.3 Hz), 23.8 (d, JPC =4.2 Hz), 23.7 (d, JPC = 5.2 Hz). 31P NMR

(160 MHz, CDCl3) δ 13.9. IR (film): 3064, 2979, 2935, 1657, 1538, 1497, 1453, 1386, 1375, 1232, 1177,

1142, 1103, 988, 897, 700, 585 cm-1. HRMS (ESI) calcd for C21H28NNaO4P, 412.1654; found412.1654.

Diethyl (3-(thiophen-2-yl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3q)

Pale yellow oil;1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 7.4 Hz, 2H), 7.57 (dd, J = 7.4, 7.4 Hz, 1H),

7.45 (dd, J = 7.7, 7.7 Hz, 2H), 4.86 - 4.84 (m, 1H), 6.74 - 4.72 (m, 1H), 5.49 (dd, J = 13.7, 2.4 Hz, 1H),

5.30 (dd, J = 13.7, 2.8 Hz, 1H), 4.72 - 4.53 (m, 2H), 3.86 (s, 1H), 3.77 (s, 1H), 2.10 (d, J = 6.5 Hz, 1H),

1.98 (d, J = 6.4Hz, 1H), 1.36(d, J = 6.2Hz, 3H), 1.33 (d, J = 6.2Hz, 3H), 1.30 (d, J = 6.2 Hz, 3H), 1.21 (d,

J = 6.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 167.3 (d, JPC= 15.5 Hz), 166.2, 143.0 (d, JPC = 1.4 Hz),

141.1 (d, JPC = 2.3 Hz), 139.9 (d, JPC = 200.5 Hz), 133.0, 130.1, 129.7, 128.4, 72.2 (d, JPC = 5.8 Hz), 70.3

(d, JPC = 5.3Hz), 70.2 (d, JPC = 5.3Hz), 61.5 (d, JPC = 2.2 Hz), 54.1 (d, JPC = 16.2 Hz), 53.5 (d, JPC =11.6

Hz), 24.1 (d, JPC = 1.9 Hz), 24.1 (d, JPC = 1.4 Hz), 24.0 (d, JPC = 3.0 Hz), 23.9 (d, JPC = 3.6 Hz). 31P NMR

(160 MHz, CDCl3) δ 13.5. IR (film): 2977, 2935, 1722, 1451, 1385, 1269, 1176, 1106, 1069, 1045, 1021,

979, 712,594 cm-1. HRMS (ESI) calcd for C21H27NaO5P, 413.1494; found 413.1493.

Diethyl [1,1'-biphenyl]-2-ylphosphonate(3r)

Pale yellow oil;1H NMR (400 MHz, CDCl3) δ 8.04 (dd, J = 14.2,7.7Hz, 1H), 7.55 (dd, J = 7.1,7.1Hz 1H),

7.44-7.31 (m, 7H), 3.97-3.78 (m, 4H), 1.12 (t, J = 6.9 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 146.0 (d,

JPC = 9.7 Hz), 141.4 (d, JPC = 4.2 Hz), 133.8 (d, JPC = 9.8 Hz), 131.9 (d, JPC = 3.0 Hz), 131.3 (d, JPC =

12

14.1 Hz) ,129.3, 127.5, 127.4, 127.0 (d, JPC = 187.3 Hz), 126.8 (d, JPC = 14.7 Hz), 61.8 (d, JPC = 6.0 Hz),

16.0 (d, JPC =6.9Hz). 31P NMR (160 MHz, CDCl3) δ 18.2. IR (film): 3056, 2981, 2929, 1467, 1444, 1390,

1242, 1163, 1139, 1094, 1056, 1024, 965, 777, 756, 701, 569, 552, 523 cm-1. HRMS (ESI) calcd for

C16H19NaO3P, 313.0970; found 313.0978.

Diethyl (4,5-dimethyl-3,6-dihydro-[1,1'-biphenyl]-2-yl)phosphonate(3s)

Pale yellow oil;1H NMR (400 MHz, CDCl3) δ 7.34 – 7.23 (m, 5H), 3.90 – 3.81 (m, 2H), 3.77 – 3.68 (m,

2H), 3.03 (d, J = 5.8 Hz, 2H), 2.93 (d, J = 6.8 Hz, 2H), 1.71 (s, 3 H), 1.64 (s, 3 H), 1.10 (t, J =7.0 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 150.1 (d, JPC = 8.6 Hz), 142.3 (d, JPC = 8.2 Hz), 127.8, 127.3 (d, JPC = 1.4

Hz), 122.7 (d, JPC = 11.0 Hz), 121.8(d, JPC = 1.8Hz), 121.5 (d, JPC = 183.6 Hz), 61.1 (d, JPC = 6.1 Hz),

42.3 (d, JPC = 16.1 Hz), 35.4 (d, JPC = 10.9 Hz), 17.8 (d, JPC = 8.6 Hz), 16.0 (d, JPC = 6.7 Hz). 31P NMR

(160 MHz, CDCl3) δ 18.8. IR (film): 3055, 2980, 2927, 2862, 1601, 1479, 1443, 1390, 1367, 1287, 1239,

1166, 1137, 1096, 1026, 966, 887, 781, 767, 751, 723, 700, 651, 635, 582, 571, 527 cm-1. HRMS (ESI)

calcd for C18H25NaO3P, 343.1439; found 343.1444.

13

1H , 13C and 31P NMR spectra of all compounds 3a

10 9 8 7 6 5 4 3 2 1 0 ppm

1.09

801.

1155

1.13

311.

1339

1.15

141.

1689

1.16

971.

1865

1.18

722.

0467

2.05

062.

0632

2.06

712.

2597

2.27

623.

8183

3.82

333.

8362

3.83

743.

8415

3.85

533.

8598

3.87

323.

8909

3.89

323.

9109

3.92

873.

9337

3.93

853.

9408

3.95

173.

9697

4.08

924.

0913

4.09

346.

9402

6.94

746.

9575

6.95

896.

9659

7.28

377.

3192

7.33

327.

3368

7.35

337.

3567

7.36

777.

3717

7.38

917.

5295

7.53

267.

5366

7.54

977.

5537

6.00

1.02

1.02

5.01

1.00

1.97

3.16

2.00

PO

O

O

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.0

116

.09

16.1

6

55.2

055

.32

58.3

958

.56

61.2

061

.26

61.4

461

.50

71.3

571

.41

76.7

377

.05

77.3

7

127.

4912

7.51

127.

8812

8.66

133.

5213

5.53

135.

5914

0.87

140.

8914

3.54

170.

5417

0.68

PO

O

O

-80-60-40-20120 100 80 60 40 20 0 ppm

17.5

7

PO

O

O

14

3b

10 9 8 7 6 5 4 3 2 1 0 ppm

2.05

202.

0558

2.05

972.

0636

2.06

862.

0725

2.07

632.

0802

2.26

362.

2673

2.27

702.

2803

2.28

373.

4592

3.48

753.

5558

3.58

393.

9454

3.94

894.

0754

4.07

714.

0796

6.93

496.

9461

6.95

326.

9565

6.95

916.

9660

6.97

757.

2835

7.30

817.

3114

7.31

487.

3210

7.32

977.

3365

7.34

347.

3471

7.35

117.

3590

7.36

257.

3735

7.37

747.

3898

7.39

447.

3991

7.51

577.

5219

7.52

507.

5291

1.02

1.02

2.94

3.00

1.01

1.02

1.97

3.10

2.02

P

O O

O

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

51.7

951

.84

52.0

752

.13

55.1

355

.25

58.4

458

.60

71.4

271

.48

76.7

677

.07

77.3

9

127.

3612

7.38

127.

9612

8.85

132.

3513

4.36

135.

3213

5.35

140.

9414

0.97

143.

51

171.

6817

1.82

P

O O

O

-80-70-60-50-40-30-20-10120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

20.5

6

P

O O

O

15

3c

10 9 8 7 6 5 4 3 2 1 0 ppm

1.06

671.

0822

1.10

821.

1237

1.20

291.

2183

1.24

981.

2573

1.26

522.

0135

2.01

722.

0209

2.02

982.

0336

2.22

002.

2364

3.92

273.

9244

3.92

654.

0861

4.08

894.

4825

4.48

674.

4979

4.50

224.

5097

4.51

764.

5252

4.52

924.

5447

6.89

426.

9024

6.90

656.

9142

6.94

826.

9556

6.95

996.

9681

7.27

157.

2899

7.30

447.

3077

7.31

117.

3297

7.33

287.

3445

7.34

857.

3660

7.36

957.

5549

7.55

737.

5609

7.56

977.

5748

7.57

86

3.08

3.01

3.03

3.12

1.10

1.03

1.03

1.05

2.03

1.01

1.00

3.13

2.04

POO

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

23.5

323

.58

23.6

723

.72

23.8

823

.92

23.9

724

.01

55.4

555

.58

58.3

158

.47

70.0

270

.07

70.1

370

.18

71.1

771

.23

127.

6512

7.76

128.

4413

4.82

135.

7313

6.83

140.

5814

3.55

169.

1216

9.27

POO

O

-80-60-40-20120 100 80 60 40 20 0 ppm

14.9

8

POO

O

16

3d

10 9 8 7 6 5 4 3 2 1 0 ppm

0.81

260.

8310

0.84

880.

8664

0.88

481.

2098

1.22

781.

2470

1.25

931.

2662

1.27

741.

2965

1.31

551.

4089

1.42

991.

4462

1.47

341.

4940

1.51

022.

0417

2.04

552.

0582

2.06

202.

2536

2.27

013.

7307

3.74

733.

7642

3.78

083.

8192

3.83

673.

8696

3.88

623.

9279

3.93

143.

9349

4.08

914.

0908

6.93

556.

9372

6.94

456.

9517

6.95

327.

3123

7.32

987.

3447

7.34

817.

3591

7.36

317.

3804

7.53

387.

5368

7.54

097.

5539

7.55

79

6.00

4.33

4.09

1.06

1.00

5.02

0.99

1.95

3.10

1.99

PO

OnBu

OnBu

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.5

613

.59

18.6

518

.71

32.2

032

.27

32.2

832

.35

55.2

755

.38

58.3

458

.50

64.9

164

.96

65.1

865

.24

71.3

471

.40

76.7

477

.06

77.3

7

127.

4812

7.49

127.

8912

8.63

133.

5313

5.53

135.

5913

5.62

140.

8714

0.90

143.

55

170.

4417

0.58

PO

OnBu

OnBu

-80-70-60-50-40-30-20-10120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.7

0

PO

OnBu

OnBu

17

3e

10 9 8 7 6 5 4 3 2 1 0 ppm

2.02

482.

0276

2.38

372.

4003

3.99

023.

9923

3.99

536.

7278

7.00

237.

0102

7.01

457.

0701

7.07

327.

0753

7.07

907.

0825

7.08

647.

2035

7.20

677.

2109

7.22

267.

2300

7.28

397.

3051

7.33

687.

3400

7.34

267.

3460

7.34

987.

3544

7.35

657.

3609

7.41

027.

4140

7.41

757.

4213

7.42

857.

4358

7.45

007.

4531

7.45

597.

4707

7.47

407.

4802

7.48

377.

5010

7.50

417.

6281

7.63

217.

6490

7.65

227.

6581

7.66

227.

6788

7.68

22

1.00

1.29

1.01

1.00

0.97

1.03

2.95

2.00

3.26

5.16

2.02

PO

Ph

Ph

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

55.8

355

.95

59.1

559

.27

71.2

971

.34

76.7

377

.04

77.3

6

127.

4012

7.60

127.

9512

8.07

128.

3212

8.44

131.

1213

1.14

131.

1713

1.21

131.

3113

1.36

131.

4113

2.51

132.

8113

3.87

135.

4813

5.52

137.

6413

8.72

141.

0214

3.10

171.

9717

2.06

PO

Ph

Ph

-80-60-40-20120 100 80 60 40 20 0 ppm

22.7

5

PO

Ph

Ph

18

3f

10 9 8 7 6 5 4 3 2 1 0 ppm

1.03

611.

0538

1.07

141.

0843

1.10

191.

1196

2.07

232.

0759

2.08

862.

0921

2.23

042.

3674

2.38

373.

7135

3.72

103.

7317

3.73

833.

7452

3.75

023.

7568

3.76

353.

7753

3.78

183.

8006

3.83

253.

8432

3.85

023.

8578

3.86

103.

8681

3.87

533.

8788

3.88

603.

8929

3.90

404.

0662

6.86

876.

8769

6.88

116.

8890

6.99

397.

0006

7.00

587.

0143

7.12

627.

1429

7.14

827.

1614

7.16

717.

1824

7.18

687.

1897

7.20

317.

2062

7.28

38

3.01

2.97

1.07

3.00

1.04

5.01

1.00

0.99

1.94

3.00

PO

O

O

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

15.9

716

.03

16.0

616

.13

20.2

0

53.7

653

.89

58.9

859

.14

61.2

561

.32

61.3

872

.53

72.5

976

.74

77.0

677

.38

125.

2712

7.44

127.

8912

9.74

135.

0613

6.00

137.

1713

7.20

138.

0314

1.14

141.

1614

3.60

171.

5317

1.67

PO

O

O

-80-70-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.0

5

PO

O

O

19

3g

10 9 8 7 6 5 4 3 2 1 0 ppm

1.08

171.

0992

1.11

671.

1355

1.13

621.

1531

1.15

381.

1714

1.99

601.

9998

2.01

252.

0163

2.19

982.

2031

2.20

652.

2160

2.21

952.

3314

3.78

403.

7920

3.80

173.

8034

3.81

023.

8211

3.82

833.

8355

3.84

593.

8478

3.85

323.

8709

3.87

323.

8838

3.89

093.

8935

3.90

703.

9250

3.93

213.

9431

3.95

044.

0391

4.04

176.

8743

6.88

596.

8933

6.90

976.

9168

6.92

086.

9285

7.13

577.

1554

7.25

997.

4171

7.42

157.

4333

7.43

75

6.02

1.01

1.03

3.02

6.06

2.00

2.01

2.00

PO OO

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

15.9

516

.02

16.0

921

.23

55.0

555

.17

58.2

358

.39

61.0

661

.11

61.3

061

.35

71.0

571

.12

76.6

877

.00

77.3

2

127.

4312

7.44

128.

4913

2.14

132.

5213

2.56

134.

1313

8.65

140.

6714

0.69

143.

41

170.

6317

0.77

PO OO

-100-80-60-40-20120 100 80 60 40 20 0 ppm

17.9

2

PO OO

20

3h

10 9 8 7 6 5 4 3 2 1 0 ppm

1.12

261.

1402

1.15

781.

1903

1.20

791.

2259

2.04

112.

0449

2.05

772.

0616

2.24

052.

2571

3.81

983.

8261

3.83

763.

8391

3.84

473.

8569

3.86

263.

8899

3.89

263.

8977

3.89

993.

9039

3.90

743.

9097

3.91

513.

9328

3.93

523.

9529

3.96

063.

9789

3.99

694.

0719

4.07

416.

9214

6.92

876.

9459

6.95

326.

9572

7.03

447.

0513

7.05

637.

0612

7.07

287.

0782

7.28

357.

5407

7.54

627.

5542

7.55

967.

5629

7.57

097.

5764

3.06

3.00

1.04

1.04

5.04

0.99

2.01

2.01

2.01

F

PO

O

O

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.0

616

.13

16.1

516

.21

55.2

255

.33

58.3

758

.53

61.2

661

.31

61.4

561

.51

71.3

171

.37

76.7

277

.04

77.3

5

114.

7811

4.99

129.

4812

9.55

129.

5613

1.61

133.

3613

5.36

140.

6214

0.64

143.

5714

3.58

161.

7016

4.17

169.

4616

9.60

F

PO

O

O

-80-60-40-20120 100 80 60 40 20 0 ppm

17.3

2

F

PO

O

O

21

3i

10 9 8 7 6 5 4 3 2 1 0 ppm

1.14

321.

1440

1.16

071.

1616

1.17

901.

1965

1.19

731.

2148

2.05

042.

0542

2.06

702.

0709

2.24

782.

2645

3.86

063.

8782

3.88

023.

8923

3.89

593.

8968

3.90

243.

9146

3.91

723.

9198

3.93

763.

9566

3.97

453.

9929

4.09

024.

0923

4.09

424.

0962

6.93

466.

9418

6.95

376.

9550

6.96

126.

9621

7.28

417.

2860

7.28

917.

2937

7.29

837.

3004

7.30

227.

4339

7.43

827.

4479

7.45

117.

4876

7.49

097.

4937

7.49

607.

4978

6.00

1.05

1.03

5.02

1.01

1.96

2.00

0.99

0.96

10 9 8 7 6 5 4 3 2 1 0 ppm

1.14

321.

1440

1.16

071.

1616

1.17

901.

1965

1.19

731.

2148

2.05

042.

0542

2.06

702.

0709

2.24

782.

2645

3.86

063.

8782

3.88

023.

8923

3.89

593.

8968

3.90

243.

9146

3.91

723.

9198

3.93

763.

9566

3.97

453.

9929

4.09

024.

0923

4.09

424.

0962

6.93

466.

9418

6.95

376.

9550

6.96

126.

9621

7.28

417.

2860

7.28

917.

2937

7.29

837.

3004

7.30

227.

4339

7.43

827.

4479

7.45

117.

4876

7.49

097.

4937

7.49

607.

4978

6.00

1.05

1.03

5.02

1.01

1.96

2.00

0.99

0.96

10 9 8 7 6 5 4 3 2 1 0 ppm

1.14

321.

1440

1.16

071.

1616

1.17

901.

1965

1.19

731.

2148

2.05

042.

0542

2.06

702.

0709

2.24

782.

2645

3.86

063.

8782

3.88

023.

8923

3.89

593.

8968

3.90

243.

9146

3.91

723.

9198

3.93

763.

9566

3.97

453.

9929

4.09

024.

0923

4.09

424.

0962

6.93

466.

9418

6.95

376.

9550

6.96

126.

9621

7.28

417.

2860

7.28

917.

2937

7.29

837.

3004

7.30

227.

4339

7.43

827.

4479

7.45

117.

4876

7.49

097.

4937

7.49

607.

4978

6.00

1.05

1.03

5.02

1.01

1.96

2.00

0.99

0.96

PO

O

OCl

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.0

716

.12

16.1

9

29.6

7

55.3

055

.42

58.2

958

.45

61.3

861

.43

61.5

861

.63

71.5

971

.65

76.7

377

.05

77.3

7

125.

8712

7.33

127.

3412

8.50

129.

1513

3.78

135.

5213

7.35

137.

3913

7.52

140.

7914

0.81

143.

56

168.

7716

8.91

PO

O

OCl

-80-70-60-50-40-30-20-10120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.6

7

PO

O

OCl

22

3j

10 9 8 7 6 5 4 3 2 1 0 ppm

1.14

821.

1777

1.19

531.

2130

2.02

492.

0282

2.04

162.

0448

2.21

932.

2359

3.76

283.

7805

3.78

803.

8001

3.80

583.

8181

3.82

503.

8364

3.84

293.

8546

3.86

173.

8720

3.89

663.

9017

3.91

453.

9217

3.93

193.

9396

3.94

463.

9520

3.96

323.

9698

3.98

113.

9883

3.99

904.

0064

4.02

424.

0552

6.88

726.

8996

6.90

716.

9239

6.93

126.

9436

7.26

007.

3976

7.41

907.

4633

7.48

47

3.00

3.06

1.02

1.00

6.06

2.00

2.02

2.00

Br

PO O

O

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.0

516

.13

16.2

0

55.2

955

.41

58.2

258

.38

61.3

361

.38

61.5

161

.57

71.4

071

.46

76.6

877

.00

77.3

2

122.

8212

9.13

129.

1513

1.03

134.

3313

4.37

134.

5013

6.49

140.

6714

0.69

143.

49

169.

2616

9.40

Br

PO O

O

-100-80-60-40-20100 80 60 40 20 0 ppm

16.9

7

Br

PO O

O

23

3k

10 9 8 7 6 5 4 3 2 1 0 ppm

1.21

401.

2316

2.06

612.

0698

2.08

312.

0867

2.24

522.

2621

3.79

023.

7978

3.81

103.

8155

3.82

923.

8332

3.83

493.

8476

3.85

313.

8658

3.87

133.

8842

3.89

863.

9157

3.92

343.

9336

3.93

613.

9411

3.95

403.

9589

3.96

133.

9768

3.97

833.

9952

4.00

194.

0132

4.02

024.

0311

4.03

854.

0565

4.08

356.

9176

6.92

986.

9370

6.94

516.

9523

6.96

457.

2600

7.62

79

6.04

0.98

1.00

6.02

1.95

3.91

PO

OO

NC

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.0

716

.14

16.1

716

.24

55.5

255

.63

58.1

658

.31

61.5

361

.58

61.6

661

.72

71.6

571

.71

76.6

977

.00

77.3

2

111.

8811

8.72

128.

1312

8.14

131.

6213

7.87

139.

8613

9.97

140.

0114

0.74

143.

54

168.

2216

8.36

PO

OO

NC

-100-80-60-40-20120 100 80 60 40 20 0 ppm

15.7

7

PO

OO

NC

24

3l

10 9 8 7 6 5 4 3 2 1 0 ppm

1.21

51.

233

1.25

11.

257

1.27

51.

292

1.99

51.

999

2.01

22.

015

2.18

92.

206

3.87

33.

891

3.89

33.

898

3.91

13.

916

3.91

83.

936

3.95

33.

966

3.97

13.

978

3.98

33.

990

3.99

64.

004

4.00

94.

012

4.02

94.

032

4.05

14.

058

4.06

14.

069

4.08

64.

094

6.82

66.

836

6.84

46.

896

6.90

36.

907

6.91

47.

075

7.08

57.

088

7.09

77.

260

7.38

77.

399

7.40

07.

825

7.83

5

6.14

1.01

1.01

6.07

1.00

1.04

1.05

1.00

0.99

S

PO

O O

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.1

416

.21

16.2

8

55.3

255

.44

58.8

859

.04

61.3

661

.41

61.4

561

.50

70.1

270

.18

76.6

977

.00

77.3

2

127.

8912

8.21

129.

3213

1.33

137.

8613

7.91

139.

8313

9.85

143.

65

162.

1016

2.24

S

PO

O O

-100-80-60-40-20120 100 80 60 40 20 0 ppm

17.3

9

S

PO

O O

25

3m

10 9 8 7 6 5 4 3 2 1 0 ppm

-0.0

001

0.89

510.

9129

0.93

081.

2542

1.27

191.

2896

1.30

121.

3091

1.31

881.

3364

1.36

211.

3832

1.40

121.

4554

1.47

061.

9233

1.93

912.

0002

2.01

612.

6033

2.60

942.

6245

2.63

182.

6383

2.64

802.

6545

2.66

052.

6705

3.55

793.

7892

3.86

493.

8707

3.88

993.

9079

3.95

113.

9690

3.97

633.

9870

3.99

434.

0050

4.01

204.

0225

4.02

454.

0381

4.04

244.

0559

6.67

616.

6876

6.69

636.

8029

6.81

046.

8146

6.82

287.

2770

3.09

10.3

0

1.04

1.04

2.05

1.01

1.02

4.01

1.00

1.01

P OO

O

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.9

116

.29

16.3

616

.41

22.5

129

.23

29.2

530

.13

30.1

5

52.9

253

.04

55.9

856

.16

60.9

861

.03

71.6

871

.74

76.7

277

.04

77.3

5

131.

4213

3.43

140.

7814

0.81

143.

28

176.

8917

7.07

P OO

O

-80-60-40-20120 100 80 60 40 20 0 ppm

18.6

5

P OO

O

26

3n

10 9 8 7 6 5 4 3 2 1 0 ppm

1.18

091.

1964

1.25

981.

2753

1.29

271.

3081

1.32

271.

3382

1.81

671.

8387

1.85

571.

8604

1.87

371.

8774

1.89

551.

9127

1.92

221.

9255

1.92

951.

9376

1.94

101.

9511

1.98

752.

0035

2.75

542.

8196

2.83

623.

4582

3.46

763.

4756

3.48

543.

4931

3.50

333.

5300

3.75

804.

4616

4.47

714.

4814

4.49

264.

4969

4.51

244.

5787

4.59

424.

5989

4.60

974.

6144

4.62

996.

6730

6.68

526.

6932

6.80

966.

8171

6.82

216.

8297

7.26

01

3.04

3.09

3.00

3.06

4.06

1.09

1.10

2.02

1.08

1.04

2.06

1.00

1.00

P O

OOCl

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

23.9

624

.01

24.0

624

.09

24.1

327

.89

27.9

230

.44

44.3

153

.04

53.1

755

.88

56.0

569

.66

69.7

171

.90

71.9

676

.68

77.0

077

.32

134.

6113

6.63

140.

3514

0.38

143.

54

172.

8917

3.07

P O

OOCl

-80-60-40-20120 100 80 60 40 20 0 ppm

15.2

4

P O

OOCl

27

3o

10 9 8 7 6 5 4 3 2 1 0 ppm

1.21

041.

2281

1.24

581.

2991

1.31

681.

3345

1.89

731.

9001

1.91

371.

9165

2.02

242.

0388

3.49

813.

5009

3.74

963.

7998

3.80

733.

8197

3.82

513.

8379

3.84

343.

8446

3.86

303.

9168

3.93

473.

9527

3.96

003.

9707

3.97

803.

9887

3.99

604.

0284

4.03

604.

0536

4.07

134.

0910

4.10

874.

1147

4.12

634.

1338

4.39

304.

4030

4.43

764.

4476

4.60

064.

6094

4.64

514.

6540

6.68

586.

6980

6.70

636.

7931

6.80

066.

8055

6.81

32

3.00

2.97

1.05

1.05

1.02

1.06

4.08

1.01

1.05

0.97

1.02

1.03

PO

OO

OH

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.1

116

.18

16.2

116

.27

53.4

453

.55

55.4

155

.58

61.7

161

.77

61.8

262

.52

62.5

671

.53

71.5

976

.68

77.0

077

.32

131.

2413

3.24

140.

5014

0.52

143.

32

177.

3717

7.55

PO

OO

OH

-100-80-60-40-20120 100 80 60 40 20 0 ppm

19.7

4

PO

OO

OH

28

3p

11 10 9 8 7 6 5 4 3 2 1 0 ppm

1.10

441.

1198

1.25

441.

2698

1.29

621.

3117

1.35

401.

3695

1.67

981.

9352

1.95

222.

0526

2.06

973.

9343

4.33

754.

3523

4.37

134.

3825

4.40

184.

4175

4.43

324.

4503

4.46

484.

4874

4.50

034.

5131

4.53

524.

5501

4.62

734.

6428

4.65

844.

6612

4.67

704.

6927

4.70

826.

7841

6.79

616.

8040

6.88

456.

8933

6.90

497.

1944

7.21

267.

2303

7.26

547.

2858

7.30

417.

3425

7.36

079.

9458

3.00

3.02

3.03

3.04

1.09

1.10

1.04

2.01

2.09

1.08

1.00

1.00

5.05

1.03

NH

CO P O

OO

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

23.7

323

.78

23.8

623

.90

23.9

523

.99

43.6

7

54.7

254

.88

56.2

256

.31

71.4

071

.44

71.4

976

.70

77.0

177

.33

126.

9612

7.94

128.

3813

8.90

141.

5914

2.58

142.

6014

2.71

144.

64

163.

0216

3.06

164.

0716

4.23

NH

CO P O

OO

-120-100-80-60-40-20120 100 80 60 40 20 0 ppm

13.8

7

NH

CO P O

OO

29

3q

11 10 9 8 7 6 5 4 3 2 1 0 ppm

1.20

601.

2214

1.25

501.

2719

1.29

671.

3122

1.32

401.

3394

1.35

221.

3676

1.97

511.

9911

2.09

112.

1073

3.76

903.

8594

4.53

204.

5475

4.56

314.

5667

4.58

244.

5979

4.61

354.

6409

4.65

644.

6719

4.67

594.

6876

4.69

174.

7072

4.72

275.

2749

5.28

215.

3091

5.31

635.

4694

5.47

555.

5036

5.50

976.

7249

6.73

656.

7446

6.83

886.

8462

6.85

046.

8583

7.26

027.

4321

7.45

107.

4704

7.55

517.

5736

7.59

218.

0421

8.06

05

3.00

9.08

0.99

0.98

1.00

0.99

2.05

1.01

1.01

0.99

0.98

1.99

1.00

2.03

CO

O PO

OO

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

23.9

223

.96

23.9

724

.00

24.1

124

.13

24.1

553

.41

53.5

253

.98

54.1

461

.49

61.5

270

.20

70.2

670

.29

70.3

472

.19

72.2

576

.68

77.0

077

.32

128.

4012

9.65

130.

1013

3.02

138.

8714

0.87

141.

0714

1.10

143.

00

166.

1916

7.18

167.

33

CO

O PO

OO

-140-120-100-80-60-40-20120 100 80 60 40 20 0 ppm

13.5

1

CO

O PO

OO

30

3r

10 9 8 7 6 5 4 3 2 1 0 ppm

1.10

381.

1212

1.13

85

3.77

973.

7982

3.82

093.

8399

3.85

823.

8763

3.89

443.

9123

3.93

093.

9350

3.95

373.

9715

7.26

007.

3077

7.32

477.

3397

7.37

027.

3869

7.39

977.

4271

7.44

007.

5346

7.55

317.

5703

8.01

218.

0313

8.04

778.

0669

6.00

4.09

7.05

1.01

0.99

PO

O

O

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

15.9

816

.05

61.7

361

.79

76.6

877

.00

77.3

2

126.

0612

6.76

126.

9012

7.39

127.

4412

7.92

129.

3213

1.26

131.

4013

1.90

133.

7313

3.83

141.

4214

1.47

145.

9914

6.08

PO

O

O

-70-60-50-40-30-20-10100 90 80 70 60 50 40 30 20 10 0 ppm

18.2

0

POO

O

31

3s

10 9 8 7 6 5 4 3 2 1 0 ppm

1.07

371.

0913

1.10

891.

6384

1.70

702.

9236

2.94

073.

0181

3.03

273.

6763

3.69

423.

7012

3.71

323.

7190

3.73

133.

7380

3.74

923.

7562

3.77

403.

8071

3.82

483.

8320

3.84

243.

8497

3.86

023.

8675

3.87

793.

8852

3.90

307.

2350

7.25

167.

2554

7.26

817.

2809

7.28

437.

3061

7.32

467.

3412

6.01

3.03

3.00

2.06

2.07

2.03

2.03

5.07

PO O

O

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.0

116

.08

17.7

817

.86

35.3

635

.47

42.1

842

.34

61.0

561

.12

76.6

877

.00

77.3

2

120.

6112

1.83

121.

8412

2.43

122.

6412

2.75

127.

2212

7.28

127.

2912

7.76

142.

2514

2.33

150.

0215

0.10

PO O

O

-100-80-60-40-20120 100 80 60 40 20 0 ppm

18.7

7

PO O

O

Documents

Catalyst–free synthesis of cycloalkenyl phosphonates · 2014-03-12 · 1 Supplementary Information for Catalyst–free synthesis of cycloalkenyl phosphonates Xunfu Xu,a Hu Chen,*ab