18 Łyz˙wa
stirred for 1 h at this temperature and sulfin-
imine 2 (1.0 mmol) in THF (5 mL) was dropped.
After stirring for 4 h at –78◦C, the reaction mixture
was quenched with a water solution of ammonium
chloride and the organic layer was separated. The
aqueous layer was extracted with ethyl ether and
combined organic layers were dried over MgSO4
and evaporated. The product of reaction (the single
diastereomer or major diastereomer) was isolated
using flash chromatography (silica gel, petroleum
ether/ethyl ether 1:1, then ethyl ether).
(CDCl3): δ 15.35, 15.77, 21.06, 21.39, 21.90, 22.65,
25.12, 31.53, 33.89, 43.10, 43.51, 48.45 (d, JCP
=
6,12Hz), 56.31 (d, JCP = 156,91Hz), 78.64 (d, JCP
=
8,09Hz), 125.24, 128.30, 129.58, 133.98, 141.62;
HRMS calcd for C34H52O4PSN (M+H) 602,8208;
found 602,3422
(–)-Di-(1S,2R,5S)-menthyl (RSSC)-1-phenyl-1-
(p-tolylsulfinylamino)-methanephosphonate 3d
[α]D = –10,3 (1,92; CHCl3), mp = 143–144◦C. 31P
1
NMR (CDCl3): 18.8; H NMR (CDCl3): δ 0.62–0.97
(m, 22H), 1.00–2.06 (m, 14H), 1.91–2.27 (m, 4H),
2.42 (s, 3H), 4.04–4.22 (m, 2H), 4.66–4.7 (m, 2H),
7.29–7.48 (m, 5H), 7.52–7.63 (m, 4H); 13C NMR
(CDCl3): δ 15.31, 15.59, 20.92, 21.31, 21.82, 22.57,
25.06, 25.17, 31.30, 31.53, 33.73, 33.85, 42.19, 43.34,
48.40 (d, JCP = 6,09 Hz), 55.89 (d, JCP = 156,7 Hz),
79.14 (d, JCP = 7,96 Hz), 125.31, 128.21, 129.50,
129.56, 129.71, 133.73, 133.86, 141.49, 141.7; HRMS:
calcd for C34H52O4PSN (M+H) 602.8208; found
602,34200.
(+)-Di-(1R,2S,5R)-menthyl(SSRC)-1-phenyl-1-
(p-tolylsulfinylamino)-methanephosphonate 3a
[α]D = +10,4 (2,24; CHCl3), melting point (mp) =
145–146◦C. 31P NMR (CDCl3): δ 18.7; 1H NMR
(CDCl3): δ 0.62–0.96 (m, 22H), 1.00–2.06 (m, 14H),
1.9–2.06 (m, 4H), 2.42 (s, 3H), 4.09–4.20 (m, 2H),
4.66–4.77 (m, 2H), 7.26–7.37 (m, 5H) 7.52–7.63
(m, 4H); 13C NMR (CDCl3): δ 15.19, 15.46, 20.80,
21.20, 21.71, 22.39, 22.45, 24.95, 25.04, 31.18, 31.40,
33.61, 33.71, 42.06, 43.21, and 48.26 (d, JCP
=
6,99Hz), 55.75 (d, J PCP = 156.61Hz), 79.00 (d, JCP
= 8,06Hz), 125.20, 128.07, 129.36, 133.64, 133.77,
141.35, and 141.59; HRMS calcd for C34H52O4PSN
(M+H) 602,8208; found 602,34257.
Hydrolysis of adducts 3 to α-APs 4
Adducts 3a or 3d (0.87mmol) were refluxed with HCl
(36%, 10 mL) for 6 h. After cooling to room temper-
ature, H2O (10 mL) was added and extracted with
CHCl3 (3 × 5 mL). The water fraction was evapo-
rated, and EtOH (5 mL) was added and neutralized
with propylene oxide. The precipitate formed was
filtered off and washed with EtOH and diethyl ether
and dried over P2O5. The pure APs 4 was obtained
as a white crystaline solid: (+)-(R)-4 (0,115g, 72%),
[α]D = +19.5 (c = 1.0, 1 M NaOH), mp 286–288◦C.
(–)-(S)-4 (0.124g, 75%), [α]D = –19.6(c = 1.07, 1M
NaOH), mp 285–288◦C.
(–)-Di-(1R,2S,5R)-menthyl (RSSC)-1-phenyl-1-
(p-tolylsulfinylamino)-methanephosphonate 3b
[α]D = –107,8 (1,29; CHCl3), oil. 31P NMR (CDCl3):
δ 18.5; 1H NMR (CDCl3): δ 0.57 (d, J = 6,89Hz,
3H), 0.62 (d, J = 6,93Hz, 3H), 0.75–0.95 (m, 14H),
0.97–1.07 (m, 4H), 1.10–1.49 (m, 4H), 1.58–1.63
(m, 4H), 1.73–2.27 (m, 4H), 2.42 (s, 3H), 4.09–
4.20 (m, 2H), 4.66–4.71 (m, 1H), 4.76 (d, J = 2.93
Hz, 1H), 7.26–7.42 (m, 5H), 7.50–7.62 (m, 4H); 13C
NMR (CDCl3): δ 15.31, 15.73, 20.97, 21.35, 21.86,
22.60, 25.08, 31.49, 33.85, 43.05, 43.46, 48.41 (d,
JCP = 6,89Hz), 56.26 (d, JCP = 156,77 Hz), 78.59
(d, JCP = 8,38Hz), 125.20, 128.27, 129.54, 129.69,
133.80, 133.93, 141.59, 141.88; HRMS calcd. for:
C34H52O4PSN (M+H) 602,8208, found 602,34268.
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(+)-Di-(1S,2R,5S)-menthyl (SSRC)-1-phenyl-1-
(p-tolylsulfinylamino)-methanephosphonate 3c
[α]D = +108,9 (0,71; CHCl3), mp = 44–46◦C. 31P
NMR (CDCl3): δ 19.1; 1H NMR (CDCl3): δ 0.57 (d, J =
6,90Hz, 3H), 0.69 (d, J = 6,9Hz, 3H), 0.78–0.86 (m,
14H), 0.91–1.17 (m, 4H), 1.18–1.35 (m, 4H), 1.58–
1.63 (m, 4H), 1.83–2.17 (m, 4H), 2.42 (s, 3H), 4.09–
4.21 (m, 2H), 4.67–4.71 (m, 1H), 4.76 (d, J = 2.91Hz,
1H), 7.29–7.42 (m, 5H), 7.51–7.63 (m, 4H); 13C NMR
[7] Łyz˙wa, P.; Błaszczyk, J.; Sieron´, L.; Mikołajczyk, M.
Eur J Org Chem 2013, 11, 2106–2115.
Heteroatom Chemistry DOI 10.1002/hc