8
Tetrahedron
PCH), 6.10-6.15 (m, 2H, HAr), 7.05 (dd, 1H, 3JPH = 40.3 Hz, 3JHH
=
Hz, CH), 7.36-7.47 (m, 4H, HAr). 13C NMR (100.6 MHz, CD3OD) δ
ACCEPTED MANUSCRIPT
8.4 Hz, CH), 7.22-7.30 (m, 2H, HAr). dia 2: 1.16-1.70 (m, 10H,
CH2), 2.28 (d, 1H, JPH = 1.8 Hz, CH3), 5.15 (dd, 1H, JPH = 7.3 Hz,
JHH = 5.1 Hz, CHOH), 6.18 (dd, 1H, JPH = 34.1 Hz, JHH = 8.4 Hz,
dia 1: 22.0 (s, CH2), 22.1 (s, CH2), 24.8 (s, CH2), 34.8 (d, JPC = 3.1
7
2
1
Hz, CH2), 37.1 (s, CH2), 71.3 (d, JPC = 116.9 Hz, CHOH), 93.2 (d,
2
3
2JPC = 2.7 Hz, C), 115.3 (d, JPC = 101.0 Hz, PCH), 128.4 (d, JPC
3.1 Hz, CH), 128.8 (d, JPC = 5.4 Hz, CH), 133.9 (d, JPC = 3.5 Hz, C),
136.6 (s, C), 159.4 (d, 2JPC = 10.3 Hz, CH). dia 2: 22.1 (s, CH2), 22.1
(s, CH2), 24.7 (s, CH2), 34.3 (d, JPC = 3.1 Hz, CH2), 36.9 (s, CH2),
=
1
3
3
PCH), 6.10-6.15 (m, 2H, HAr), 7.15 (dd, 1H, JPH = 40.1 Hz, JHH
=
8.4 Hz, CH), 7.22-7.30 (m, 2H, HAr). 13C NMR (100.6 MHz, DMSO-
D6) δ dia 1: 20.7 (s, CH3), 21.7 (s, CH2), 21.7 (s, CH2), 24.3 (s,
CH2), 34.2 (d, JPC = 2.9 Hz, CH2), 36.5 (s, CH2), 71.5 (d, JPC
115.6 Hz, CHOH), 90.7 (d, JPC = 2.2 Hz, C), 117.2 (d, JPC = 98.1
Hz, PCH), 127.0 (d, JPC = 5.1 Hz, CH), 128.4 (d, JPC = 2.2 Hz, CH),
135.1 (d, JPC = 2.2 Hz, C), 136.4 (d, JPC = 4.3 Hz, C), 160.0 (d, JPC
1
1
2
=
70.8 (d, JPC = 117.3 Hz, CHOH), 93.5 (d, JPC = 1.9 Hz, C), 117.7
2
1
1
(d, JPC = 101.6 Hz, CH), 128.2 (d, JPC = 2.7 Hz, CH), 129.2 (d, JPC
= 5.0 Hz, CH), 136.4 (d, JPC = 3.1 Hz, C), 136.6 (s, C), 158.9 (d, 2JPC
= 10.0 Hz, CH). HRMS (FAB) m/z calcd for C15H19ClO3P (M+H)+,
313.0760; found, 313.0764. IR (NaCl): 3184, 2947, 2850, 2386,
1577, 1493, 1448, 1406, 1322, 1259, 1208, 1158, 1091, 1064, 1013,
943, 873, 831, 812, 738, 643, 563, 540.
2
= 10.2 Hz, CH). dia 2: 20.7 (s, CH3), 21.6 (s, CH2), 21.6 (s, CH2),
24.2 (s, CH2), 33.8 (d, JPC = 2.2 Hz, CH2), 36.3 (s, CH2), 70.5 (d,
1JPC = 114.9 Hz, CHOH), 90.5 (d, 2JPC = 2.2 Hz, C), 117.3 (d, 1JPC
=
98.8 Hz, PCH), 127.2 (d, JPC = 5.1 Hz, CH), 128.2 (d, JPC = 2.2 Hz,
2
2
CH), 135.4 (s, C), 136.4 (d, JPC = 3.7 Hz, C), 156.4 (d, JPC = 9.5
Hz, CH). HRMS (FAB) m/z calcd for C16H22O3P (M+H)+, 293.1306;
found, 293.1303. IR (NaCl): 3418, 1651, 1203, 1106, 1064, 942,
904, 813, 740, 631, 552.
C15H18ClO3P
MW 312.73, 680 mg, yield 75%, white
solid, melting point: 183°C. de = 4 %.
C16H21O3P
4.6.6. 2-([1,1'-biphenyl]-4-yl(hydroxy)methyl)-1-oxa-2-phosphaspiro
[4.5]dec-3-ene 2-oxide (14f). White solid, 0.770g, 75% yield, de =
18%. 31P NMR (101.2 MHz, CDCl3): δ 64.6 (59%, dia 1), 62.5
(41%, dia 2). one diastereomer was separated 1H NMR (400.1 MHz,
MW 292.31, 700 mg, yield 83%, white
solid, melting point: 170°C. de = 12%.
2
CDCl3) δ dia 1: 1.33-1.88 (m, 10H, CH2), 5.10 (d, JPH = 5.8 Hz,
2
3
4.6.4. 2-(Hydroxy(4-(trifluoromethyl)phenyl)methyl)-1-oxa-2-phos-
phaspiro[4.5]dec-3-ene 2-oxide (14d). White solid, 0.830g, 83%
yield, de = 22%. 31P NMR (101.2 MHz, CD3OD): δ 61.9 (39%, dia
1), 64.1 (61%, dia 2). 19F NMR (188.3 MHz, CD3OD) δ -61.3; 1H
NMR (400.13 MHz, DMSO-d6) δ dia 1: 1.39-1.87 (m, 10H, CH2),
CHOH), 5.98 (dd, JPH = 33.8 Hz, JHH = 8.5 Hz, PCH), 6.89 (dd,
3JPH = 39.6 Hz, JHH = 8.5 Hz, CH), 7.24-7.49 (m, 9H, HAr). dia 2:
3
1.33-1.88 (m, 10H, CH2), 5.10 (d, 2JPH = 11.9 Hz, CHOH), 6.09 (dd,
2JPH = 32.8 Hz, JHH = 8.5 Hz, PCH), 6.73 (dd, JPH = 39.4 Hz, JHH
= 8.53 Hz, CH), 7.24-7.49 (m, 9H, HAr). 13C NMR (101 MHz,
CDCl3) δ 21.9 (s, CH2), 21.9 (s, CH2), 24.7 (s, CH2), 34.3 (d, J = 3.4
3
3
3
2
2
5.14 (d, 1H, JPH = 11.8 Hz, CHOH), 6.16 (dd, 1H, JPH = 34.6 Hz,
Hz, CH2), 36.9 (s, CH21), 72.7 (d, 1J = 113.5 Hz, CHO), 92.7 (d, J =
2
3JHH = 8.5 Hz, PCH), 7.18-7.26 (m, 2H, HAr), 7.39 (dd, 1H, JPH
=
3
3
1.4 Hz, C), 116.2 (d, J = 101.7 Hz, PCH), 126.8 (d, J = 2.8 Hz,
CHAr), 127.1 (s, CHAr), 127.4 (s, CHAr), 127.8 (d, J = 5.3 Hz, CHAr),
128.9 (s, CHAr), 135.8 (s, CAr), 140.8 (s, J = 1.4 Hz, CAr), 140.8 (d, J
= 3.7 Hz, CAr), 157.3 (d, 2J = 10.9 Hz, CH). HRMS (FAB) m/z calcd
for C21H24O3P (M+H)+, 355.1463; found, 355.1463. IR (NaCl):
3410, 2959, 1661, 1605, 1433, 1261, 1102, 1051, 949, 749, 694.
39.9 Hz, JHH = 8.5 Hz, CH), 7.54-7.60 (m, 2H, HAr). dia 2: 1.39-
2
1.87 (m, 10H, CH2), 5.24 (d, 1H, JPH = 7.2 Hz, CHOH), 6.31 (dd,
2
3
1H, JPH = 34.8 Hz, JHH = 8.5 Hz, PCH), 7.18-7.26 (m, 2H, HAr),
7.31 (dd, 1H, 3JPH = 40.1 Hz, 3JHH = 8.5 Hz, CH), 7.54-7.60 (m, 2H,
HAr). 13C NMR (100.6 MHz, CD3OD) δ dia 1: 21.8 (s, CH2), 21.9 (s,
CH2), 24.6 (s, CH2), 34.7 (d, JPC = 2.9 Hz, CH2), 37.0 (s, CH2), 72.2
1
2
(d, JPC = 109.8 Hz, CHOH), 92.7 (d, JPC = 2.2 Hz, C), 116.1 (d,
1JPC = 101.0 Hz, PCH), 124.4 (d, JCF = 272.2 Hz, CF3), 125.1 (qd,
1
C21H23O3P
JCF = 8.0 Hz, JPC = 5.1 Hz, CH), 127.2 (d, JPC = 5.1 Hz, CH), 140.8
(s, C), 158.3 (d, JPC = 11.7 Hz, CH). dia 2: 22.0 (s, CH2), 22.0 (s,
CH2), 24.5 (s, CH2), 34.1 (d, JPC = 3.6 Hz, CH2) 36.8 (s, CH2), 72.2
2
MW 354.39, 770 mg, yield 75%, white
solid, melting point: 150°C. de = 4 %.
1
2
(d, JPC = 112.7 Hz, CHOH), 93.0 (d, JPC = 1.5 Hz, C), 115.7 (d,
1JPC = 102.5 Hz, PCH), 124.4 (d, JCF = 272.2 Hz, CF3), 124.9 (qd,
1
JCF = 8.3 Hz, JPC = 5.2 Hz, CH), 127.5 (d, JPC = 5.1 Hz, CH), 141.0
2
2
(d, JPC = 1.5 Hz, C), 157.6 (d, JPC = 11.0 Hz, CH). HRMS (FAB)
m/z calcd for C16H19F3O3P (M+H)+, 347.1024; found, 347.1020. IR
(NaCl): 3211, 2936, 2862, 1620, 1583, 1455, 1416, 1325, 1227,
1204, 1163, 1126, 1120, 1067, 1016, 940, 907, 837, 814, 737, 606,
555.
4.6.7. 2-(hydroxy(2-nitrophenyl)methyl)-1-oxa-2-phosphaspiro[4.5]-
dec-3-ene 2-oxide (14g). The two diastereomers were separated by
chromatrography on silica-gel. White solid, 0.770g, 63%, de = 14%.
1
Dia 1: 254 mg. 31P NMR (101.2 MHz, CDCl3): δ 64.3; H NMR
2
(250.1 MHz, CDCl3) δ 0.85-1.69 (m, 10H, CH2), 6.33 (dd, 1H, JPH
3
2
= 30.3 Hz, JHH = 8.4 Hz, PCH), 6.53 (d, 1H, JPH = 18.0 Hz,
CHOH), 6.82 (dd, 1H, 3JPH = 41.0 Hz, 3JHH = 8.4 Hz, CH), 7.42-7.46
(m, 1H, CHAr), 7.63-7.69 (m, 1H, CHAr), 7.90-7.92 (m, 1H, CHAr),
C16H18F3O3P
MW 346.29, 830 mg, yield 83%, white
solid, melting point: 158°C. de = 22 %.
3
8.22 (d, 1H, JHH = 8.2 Hz, CHAr). 13C NMR (50.3 MHz, CDCl3) δ
21.7 (s, CH2), 21.8 (s, CH2), 24.6 (s, CH2), 34.5 (d, JPC = 3.7 Hz,
1
2
CH2), 37.0 (s, CH2), 70.3 (d, JPC = 117.6 Hz, CHOH), 92.8 (d, JPC
1
= 1.5 Hz, C), 116.4 (d, JPC = 108.3 Hz, PCH), 124.9 (d, JPC = 2.2
4.6.5. 2-((4-Chlorophenyl)(hydroxy)methyl)-1-oxa-2-phosphaspiro
[4.5]dec-3-ene 2-oxide (14e). White solid, 0.680g, 75% yield, de =
4%. 31P NMR (101.2 MHz, CD3OD): δ 66.2 (48%, dia 1), 66.6
(52%, dia 2). 1H NMR (400.1 MHz, CD3OD) δ dia 1: 1.32-1.80 (m,
Hz, CH), 128.1 (d, JPC = 3.7 Hz, CH), 128.7 (d, JPC = 5.1 Hz, CH),
133.9 (d, JPC = 2.9 Hz, CH), 135.2 (s, C), 146.5 (d, JPC = 5.1 Hz, C),
2
156.7 (d, JPC = 13.2 Hz, CH). HRMS (FAB) m/z calcd for
C15H19NO5P (M+H)+, 324.1001; found, 324.1008. IR (NaCl): 3172,
2939, 1525, 1340, 1222, 1192, 1156, 937, 856, 735, 555.
2
2
10H, CH2), 5.05 (d, 1H, JPH = 12.3 Hz, CHOH), 6.06 (dd, 1H, JPH
= 34.8 Hz, 3JHH = 8.4 Hz, PCH), 7.31 (dd, 1H, 3JPH = 40.1 Hz, 3JHH
8.4 Hz, CH), 7.36-7.47 (m, 4H, HAr). dia 2: 1.32-1.80 (m, 10H,
1
Dia 2: 336 mg. 31P NMR (101.2 MHz, CDCl3): δ 65.5; H NMR
=
2
(250.1 MHz, CDCl3) δ 0.90-1.80 (m, 10H, CH2), 6.23 (dd, 1H, JPH
2
2
3
2
CH2), 5.15 (d, 1H, JPH = 7.6 Hz, CHOH), 6.2 (dd, 1H, JPH = 34.8
= 31.5 Hz, JHH = 8.4 Hz, PCH), 6.45 (d, 1H, JPH = 15.4 Hz,
CHOH), 7.04 (dd, 1H, 3JPH = 43.2 Hz, 3JHH = 8.4 Hz, CH), 7.44-7.45
3
3
3
Hz, JHH = 8.4 Hz, PCH), 7.21 (dd, 1H, JPH = 40.3 Hz, JHH = 8.4