Page 11 of 15
New Journal of Chemistry
DOI: 10.1039/C7NJ03345A
JPC = 4.9 Hz, CH2), 37.74 (d, JPC = 14.4 Hz, CHCH3), 59.52 (d, , JP-C = 158 Hz, CHP), 62.30
(d, JPC = 6.60 Hz, POCH2CH3), 62.60 (OC(CH3)3), 62.65 (d, JPC = 6.60 Hz, POCH2CH3),
127.95 (Ph), 128.41 (Ph), 128.45 (Ph), 128.57 (Ph), 128.71 (Ph), 128.84 (Ph), 128.86 (Ph),
128.93 (Ph), 130.18 (Ph), 130.28 (Ph), 135.70 (Ph), 135.74 (Ph), 137.53 (Ph), 139.58 (Ph),
169.72 (CN), 175.44 (CO), 31P NMR (121 MHz): δ (ppm) : 24.0.
[1Sꢀ(Benzhydrylideneꢀamino)ꢀ3Rꢀcyanoꢀ3ꢀmethylꢀpropyl]ꢀphosphonic acid diethyl
ester (4g). Colorless oil. [α] 2D0 = 17.1 (c 0.8, CHCl3). HPLC conditions: Chiralpack ADꢀH
(hexaneꢀIPA 95:5, flow rate: 0.8 mL/min, 256 nm, 5°C) major diastereomer: tmajor = 53.4 min
and tminor = 22.5 min; minor diastereomer: tmajor = 27.7 min and tminor = 69.2 min. Major
diastereomer: 1H NMR (500 MHz): δ (ppm): 1.02 (d, J = 7.0 Hz, 3H), 1.24 (t, J = 7.0 Hz, 3
H), 1.28 (t, J = 7.1 Hz, 3 H), 1.98ꢀ2.10 (m, 1H), 2.22ꢀ2.70 (m, 2 H), 3.88ꢀ4.00 (m, 1 H), 4.00ꢀ
4.20 (m, 2 H), 7.19ꢀ7.62 (m, 10 H). 13C NMR (60 MHz): δ (ppm): 16.53, (OCH2CH3), 16.60,
(OCH2CH3), 18.63 (CH3), 23.02 (d, JPC = 16.2 Hz, CHCH3), 36.34 (d, JPC = 4.3 Hz, CH2),
59.14 (d, JPC = 157.34 Hz, CHP), 62.78 (d, JPC = 7.89 Hz, POCH2CH3), 65.40 (d, JPC = 6.54
Hz, POCH2CH3), 122.68 (CHCN), 128.13 (Ph), 128.32 (Ph), 128.46 (Ph), 128.48 (Ph),
128.48 (Ph), 128.56 (Ph), 128.68 (Ph), 128.90 (Ph), 128.91 (Ph), 129.0 (Ph), 129.08 (Ph),
130.1 (Ph), 130.65 (Ph), 132.46 (Ph), 135.06 (Ph), 135.32 (Ph), 139.12 (Ph), 139.25 (Ph),
1
171.90 (CN). 31P NMR (121 MHz): δ (ppm): 22.8. Minor diastereomer: H NMR (500
MHz): δ (ppm): 1.18 (d, J = 7.1 Hz, 3 H), 1.23 (t, J = 7.1 Hz, 3 H), 1.29 (t, J = 7.1 Hz, 3 H),
1.98ꢀ2.10 (m, 1H), 2.22ꢀ2.70 (m, 2 H), 3.88ꢀ4.0 (m, 1 H), 4.0ꢀ4.2 (m, 2 H), 7.19ꢀ7.62 (m, 10
H). 13C NMR (60 MHz): δ (ppm): 16.53, (OCH2CH3), 16.60, (OCH2CH3), 17.70 (CH3), 22.69
(d, JPC = 15.2 Hz, CHCH3), 35.94 (d, JPC = 4.8 Hz, CH2), 59.20 (d, JPC = 159.09 Hz, CHP),
62.87 (d, JPC = 4.41 Hz, POCH2CH3), 62.97 (d, JPC = 4.0 Hz, POCH2CH3), 122.04 (CHCN),
128.13 (Ph), 128.32 (Ph), 128.46 (Ph), 128.48 (Ph), 128.48 (Ph), 128.56 (Ph), 128.68 (Ph),
128.90 (Ph), 128.91 (Ph), 129.0 (Ph), 129.08 (Ph), 130.1 (Ph), 130.65 (Ph), 132.46 (Ph),
135.06 (Ph), 135.32 (Ph), 139.12 (Ph), 139.25 (Ph), 172.61 (CN). 31P NMR (121 MHz): δ
(ppm): 22.8. MS (ESI): m/z = 399.18296 [M+H]+. Calcd. for C22H28N2O3P: 399.18321.
[1ꢀ(Benzhydrylideneꢀamino)ꢀ3ꢀcyanoꢀ2ꢀphenylꢀpropyl]ꢀphosphonic acid diethyl
ester (4h) Colorless oil. HPLC conditions: Chiralpack ADꢀH (hexaneꢀIPA 95:5, flow rate: 1
ml/min, 256 nm, 5°C) major diastereomer: tmajor = 32.7 min and tminor = 62.8 min; minor
1
diastereomer: tmajor = 27.7 min and tminor = 69.2 min. Major diastereomer: H NMR (500
MHz): δ (ppm): 1.24 (t, J = 7.05 Hz, 3 H), 1.29 (t, J = 7.03 Hz, 3 H), 3.30 (dd, JHaHb = 17.22
Hz, JHH = 5.59 Hz, 1H), 3.55 (dd, JHaHb = 17.22 Hz, JHH = 3.98 Hz, 1H), 3.71ꢀ3.80 (m, 1H),
3.99ꢀ4.16 (m, 5 H), 7.04ꢀ7.62 (m, 15 Har). 13C NMR (60 MHz): δ(ppm): 16.7, (d, JPC = 5,71
Hz, CH3), 16.7, (d, JPC = 5,66 Hz, CH3), 18.7 (d, JPC = 4.03 Hz, CH2), 44.0 (d, JPC = 3.42 Hz,
CHPh), 62.9 (d, JPC = 7.0 Hz, OCH2), 63.1 (d, JPC = 7.21 Hz, OCH2), 65.4 (d, JPC = 155.45
Hz, CHP), 119.6 (CH2CN), 127.8 (Ph), 127.8 (Ph), 127.8 (Ph), 128.2 (Ph), 128.4 (Ph), 128.4
(Ph), 128.6 (Ph), 128.9 (Ph), 129.0 (Ph), 129.5 (Ph), 131.0 (Ph), 135.0 (d, JPC = 2,63 Hz,
CArq), 139.1 (d, JPC = 3,73 Hz, CArq), 139.3 (d, JPC = 13.97 Hz, CArqCH), 172.9 (d, JPC = 15,59
1
Hz, Ph2CN). 31P NMR (121 MHz): δ (ppm): 21.80. Minor diastereomer: H NMR (500
MHz): δ (ppm): 1.10 (t, J = 7.03 Hz, 3 H), 1.14 (t, J = 7.0 Hz, 3H), 2.85 (dd, JHaHb = 16.52
Hz, JHH = 9.80 Hz, 1H), 3.10 (dd, JHaHb = 16.52 Hz, JHH = 4.0 Hz, 1H), 3.51ꢀ3.58 (dd, JHaHb
=
13.25 Hz, JHH = 3.98 Hz, 1H), 3.71ꢀ3.8 (m, 1H), 3.99ꢀ4.16 (m, 5 H), 7.04ꢀ7.62 (m, 15 Har).
13C NMR (60 MHz): δ (ppm): 16.4, (d, JPC = 6.11 Hz, CH3), 16.5, (d, JPC = 6.12 Hz, CH3),
18.7 (d, JPC = 4.03 Hz, CH2), 50.1 (d, JPC = 16.17 Hz, CHPh), 62.9 (d, JPC = 7 Hz, OCH2),
63.1 (d, JPC = 7.21 Hz, OCH2), 59.8 (d, JPC = 168.87 Hz, CHP, 127.8 (Ph), 127.8 (Ph), 127.8
(Ph), 128.2 (Ph), 128.4 (Ph), 128.4 (Ph), 128.6 (Ph), 128.9 (Ph), 129.0 (Ph), 129.0 (Ph), 131.0