ENANTIOSELECTIVE ADDITION OF β-KETO PHOSPHINATE TO ω-NITROSTYRENE
155
3
Methyl 2-{2-[methoxy(phenyl)[phosphoryl]-1-
phenyl-ethylidene}hydrazinecarboxylate (2). To a
boiling solution of 7.3 g (0.043 mol) of O,O-dimethyl-
phenylphosphonite in 58 mL of toluene was added
within 40 min under argon by small portions 10.5 g
(0.039 mol) of methyl 2-(2-bromo-1-phenylethylidene)-
hydrazinecarboxylate 1. After adding the total neces-
sary amount of compound 1 the mixture was stirred for
3 h. The reaction mixture was cooled, solid phosphi-
nate 2 was filtered off, washed with a little toluene,
and dried in air. Yield 9.0 g (67%), colorless crystals,
mp 124–125°С. IR spectrum, ν, cm–1: 3227 w (NH),
3046 w (CHaryl), 2947 w (CHaliph), 2843 w (CHaliph),
1746 s (C=O), 1593 w (С–Сaryl), 1541 s (С=N), 1445
m (C–N), 1223 v.s (P=O), 1030 s (P–O–C), 739 s
133 Hz), 131.98 d (Ph, 2CmH, JCP 11 Hz), 132.92 d
(Ph, CpH, 4JCP 3 Hz), 136.75 (CH, Ph), 192.10 d (С=O,
2JCP 5 Hz). 31P NMR spectrum, δ, ppm: 36.98. Found,
%: С 65.74; Н 5.53. C15H15O3P. Calculated, %: С
65.69; Н 5.51.
Methyl [(S,2R,3S)-4-nitro-1-oxo-1,3-diphenyl-
butan-2-yl](phenyl)phosphinate (6). To a solution of
0.3 g (1.0 mmol) of compound 3 and 0.22 g (1.05 mmol)
of ω-nitrostyrene in 2 mL of toluene was added 0.016 g
(2 × 10–5 mol) of dibromobis[(1R,2R)-N,N'-dibenzyl-
cyclohexane-1,2-diamine]nickel(II) 5 and the mixture
was left standing at room temperature for 36 h. The
separated precipitate was filtered off, the reaction
product was purified by recrystallization. Yield 0.12 g
(28%), colorless crystals, ee 92%, mp 197–200°С
(from methanol), [α]D20 +115.6 (c 1.0, CHCl3). IR spec-
trum, ν, cm–1: 3051 w (CHaryl), 2949 w (CHaliph), 2847
w (CHaliph), 1674 s (C=O), 1597 w (С–Сaryl), 1546 v.s
(С–NO2), 1385 m (С–NO2), 1231 v.s (P=O), 1035 s
1
(CHaryl). Н NMR spectrum, δ, ppm: 3.37 d.d (1H,
2
2
2
CH2, JHH 14.7, JHP 19 Hz), 3.53 d.d (1H, CH2, JHH
2
3
14.6, JHP 19 Hz), 3.67 d (3H, MeOP, JHP 11.2 Hz),
3.85 s [3H, MeOC(O)], 7.22–7.28 m (3H, Ph), 7.42–
7.47 m (2H, Ph), 7.53–7.58 m (3H, Ph), 7.74–7.79 m
(2H, Ph), 10.53 br.s (1H, NH). 13C NMR spectrum
(100 MHz), δ, ppm: 32.78 d (CH2, 1JCP 91.5 Hz), 52.33
d (MeOP, 2JCP 2 Hz), 52.92 [MeOC(O)], 126.63 (2CH,
Ph), 128.28 d (Ph, Ci, 1JCP 130 Hz), 128.34 (2CH, Ph),
1
(P–O–C), 858 w (С–N), 740 s (CHaryl). Н NMR
spectrum, δ, ppm: 3.49 d (3H, CH3, 3JHP 11.2 Hz), 4.26–
3
4.29 m (1H, CHPh), 4.67 d.d [1H, CHP(O), JHH 6,
2JHP 16 Hz], 5.06 d.d (1H, CH2, JHH 10, JHH 14 Hz),
3
2
3
2
5.24 d.d (1H, CH2, JHH 3, JHH 14 Hz), 7.00–7.03 m
(2H, Ph), 7.06–7.12 m (3H, Ph), 7.37–7.41 m (4H, Ph),
7.50–7.59 m (4H, Ph), 7.72–7.75 m (2H, Ph). 13C
NMR spectrum (100 MHz), δ, ppm: 52.04 d (OMe,
2
129.15 (CH, Ph), 129.22 d (Ph, 2CoH, JCP 37 Hz),
3
131.75 d (Ph, 2CmH, JCP 10 Hz), 133.47 d (Ph, CpH,
4
4JCP 3 Hz), 137.41 d (Ph, Ci, JCP 4 Hz), 144.94 d
(C=N, 2JCP 10.5 Hz), 155.85 (C=O). 31P NMR spectrum,
δ, ppm: 42.17. Found, %: С 58.74; Н 5.61; N 8.07.
C17H19N2O4P. Calculated, %: С 58.96; Н 5.53; N 8.09.
2JCP 5.7 Hz), 53.36 d [CHP(O), JCP 84 Hz], 78.18
1
(CH2), 127.88 (2CH, Ph), 128.27 (CH, Ph), 128.55
(2CH, Ph), 128.75 (2CH, Ph), 128.78 d (Ph, Ci, JCP
1
129.3 Hz), 128.98 d (Ph, 2CoH, JCP 13 Hz), 128.99
2
Methyl 2-oxo-2-phenyl-2-ethyl(phenyl)phosphi-
nate (3). To 8.0 g (0.023 mol) of compound 2 in 13 mL
of acetone was added 13 mL of 3 M solution of
hydrochloric acid and the mixture was stirred at room
temperature for 3.5 h. The organic layer was separated.
Acetone was evaporated from the water layer in a
vacuum, the reaction product was extracted with
chloroform (3 × 50 mL). Extract was dried with
calcium chloride, chloroform was evaporated in a
vacuum. Yield 6.0 g (94%), light yellow oil. IR
spectrum, ν, cm–1: 3048 w (CHaryl), 2947 w (CHaliph),
2843 w (CHaliph) 1672 s (C=O), 1597 w (С–Сaryl), 1226
(2CH, Ph), 132.05 d (Ph, 2CmH, JCP 10 Hz), 133.07 d
3
(Ph, CpH, JCP 3 Hz), 133.72 (CH, Ph), 137.47 d (Ph,
4
Ci, JCP 9.5 Hz), 138.03 (Ci, Ph), 197.68 (C=O). 31P
3
NMR spectrum, δ, ppm: 38.01. Found, %: С 65.35; Н
5.17; N 3.30. C23H22NO5P. Calculated, %: С 65.24; Н
5.24; N 3.31.
HPLC analysis. Column Chiralpak AD-3, eluent
hexane–2-propanol, 80 : 20, flow rate 1.2 mL/min,
wavelength 210 nm): tr 13.98 [(R,2S,3R)-isomer],
25.26 [(S,2R,3S)-isomer] min.
1
v.s (P=O), 1030 s (P–O–C), 740 s (CHaryl). Н NMR
XRD analysis. C15H15O3P, M 423.38, crystals
monoclinic, space group P21, a 5.7841(5), b 13.7403(11),
c 13.3076(13) Å, α = γ = 90, β 96.625(8) deg; V
1050.56(16) Å3, dcalc 1.338 mg/m3, Z 2, F(000) 444, l
1.5418 Å, m 1.457 mm–1, total reflections/unique
reflections 3892/2913 (Rint 0.0000), T 295(2) K, Θ 4.65–
72.76 deg, R1 0.0732, ωR2 0.1121 for [I > 2σ(I)], R1
0.0549, ωR2 0.1009 for all reflections, Flack parameter
spectrum, δ, ppm: 3.62 d (3H, CH3, 3JHP 11.4 Hz), 3.75
2
2
d.d (2H, CH2, JHH 1, JHP 20 Hz), 7.34–7.42 m (4H,
Ph), 7.47–7.51 m (2H, Ph), 7.69–7.75 m (2H, Ph), 7.87–
7.90 m (2H, Ph). 13C NMR spectrum (100 MHz), δ,
1
2
ppm: 42.57 d (CH2, JCP 86.8 Hz), 51.82 d (OMe, JCP
3.8 Hz), 128.64 (CH, Ph), 128.77 d (Ph, 2CoH, JCP
2
13.5 Hz), 129.12 (CH, Ph), 129.37 d (Ph, Ci, JCP
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 2 2017