1668
M. Mąkosza, D. Sulikowski
LETTER
(19) (a) Mąkosza, M.; Glinka, T.; Kinowski, A. Tetrahedron
1984, 40, 1863. (b) Mąkosza, M.; Wenall, M.; Goliński, J.;
Kinowski, A. Bull. Pol. Acad. Chem. 1985, 33, 427.
(20) Selected Analytical Data
(13) (a) Counotte-Potman, A.; van der Plas, H. C. J. Heterocycl.
Chem. 1981, 18, 123. (b) Van der Plas, H. C.; Woźniak, M.
Croat. Chim. Acta 1986, 59, 33. (c) Woźniak, M.;
van der Plas, H. C. Acta Chem. Scand. 1993, 47, 95.
(d) Stern, K. M.; Cheng, B. K.; Hilman, F. D.; Allman, J. M.
J. Org. Chem. 1994, 59, 5627.
Diethyl N-(1,3-Ditiholan-2-ylidene)-a-(2-nitrophenyl)-
phosphoglycinate (2a)
(14) Mąkosza, M.; Paszewski, M.; Sulikowski, D. Synlett 2008,
2938.
(15) (a) Mąkosza, M.; Surowiec, M.; Szczepańska, A.;
Sulikowski, D.; Maltsev, O. Synlett 2007, 470.
Solidifying oil. IR (film, CH2Cl2): nmax = 2986, 2905, 1589,
1534, 1355, 1245, 1026, 572 cm–1. 1H NMR (400 MHz,
CDCl3): d = 8.00 (m, 1 H), 7.90 (m, 1 H), 7.61 (m, 1 H), 7.41
(m, 1 H), 4.50 (s, 1 H), 5.96 (d, J = 18.8 Hz), 4.11–4.00 (m,
4 H), 3.64–3.40 (m, 4 H), 1.26–1.21 (m, 6 H). 13C NMR (100
MHz, CDCl3): d = 175.6 (d, J = 19 Hz), 148.4 (d, J = 7 Hz),
132.9 (d, J = 4 Hz), 130.9 (d, J = 7 Hz), 130.7 (d, J = 4 Hz),
128.1 (d, J = 4 Hz), 124 (d, J = 3 Hz), 65.9 (d, J = 156 Hz),
63.4 (d, J = 15 Hz), 63.3 (d, J = 15 Hz), 38.1, 35.0, 16.3 (d,
J = 10 Hz), 16.2 (d, J = 10 Hz). 31P NMR (162 MHz,
CDCl3): d = 18.1. ESI-LRMS (+): m/z 391 [M + H]+. Anal.
Calcd for C14H19N2O5S2P: C, 43.07; H, 4.91; N, 7.18; S,
16.43. Found: C, 42.85; H, 4.90; N, 7.17; S, 16.55.
Diethyl N-(1,3-Dithiolan-2-ylidene)-a-(1-nitro-2-naphthyl)-
phosphoglycinate (9b)
Oil. IR (film, CH2Cl2): nmax = 2983, 1581, 1528, 1254, 1049,
1020, 563 cm–1. 1H NMR (400 MHz, CDCl3): d = 8.05–7.95
(m, 2 H), 7.90–7.85 (m, 1 H), 7.76–7.71 (m, 1 H), 7.63–7.54
(m, 2 H), 5.15 (d, J = 18.0 Hz), 4.20–4.00 (m, 4 H), 3.65–
3.51 (m, 2 H), 3.49–3.35 (m, 2 H), 1.28 (dt, J = 0.4, 7.1 Hz,
3 H), 1.22 (dt, J = 0.4, 7.1 Hz, 3 H). 13C NMR (100 MHz,
CDCl3): d = 175.7 (d, J = 19 Hz), 146.8 (d, J = 9 Hz), 133.0
(d, J = 2 Hz), 130.6 (d, J = 3 Hz), 128.4, 127.9 (d, J = 2 Hz),
127.4, 126.2 (d, J = 4 Hz), 126.0 (d, J = 6 Hz), 124.2 (d,
J = 2 Hz), 121.8, 66.9 (d, J = 161 Hz), 63.6 (d, J = 8 Hz),
63.5 (d, J = 8 Hz), 38.2, 34.9, 16.2 (d, J = 6 Hz), 16.1 (d,
J = 6 Hz). 31P NMR (162 MHz, CDCl3): d = 17.6. ESI-
LRMS (+): m/z 463 [M + H]+. Anal. Calcd for
(b) Mąkosza, M.; Sulikowski, D.; Maltsev, O. Synlett 2008,
1711. (c) Mąkosza, M.; Staliński, K. Chem. Eur. J. 1997, 3,
2025. (d) Mąkosza, M.; Staliński, K. Synthesis 1998, 1631.
(e) Mąkosza, M.; Staliński, K. Tetrahedron 1998, 54, 8797.
(f) Mąkosza, M.; Staliński, K. Pol. J. Chem. 1999, 73, 151.
(g) Mąkosza, M.; Kamieńska-Trela, K.; Paszewski, M.;
Bechcicka, M. Tetrahedron 2005, 61, 11952. (h) Bartoli, G.
Acc. Chem. Res. 1984, 17, 109. (i) Mąkosza, M.;
Sypniewski, M. Tetrahedron 1994, 50, 4913. (j) Mąkosza,
M.; Paszewski, M. Synthesis 2002, 2203. (k) Mąkosza, M.;
Sulikowski, D. J. Org. Chem. 2009, 74, 3827. (l) Bartoli,
G.; Bosco, M.; Melandri, A.; Boicelli, C. J. Org. Chem.
1979, 44, 2087.
(16) (a) Oberhauser, T.; Meduna, V. Tetrahedron 1996, 52,
7691. (b) Modified Literature Procedure16c
To the solution of diethyl phosphoglycinate (4.55 g, 27.2
mmol) in CHCl3 (100 mL) Et3N (3 equiv, 81.6 mmol, 12.5
mL) was added followed by CS2 (1.5 equiv, 40.8 mmol, 2.43
mL). The resulting mixture was stirred at r.t. for 24 h, and
then ethylene bromide (1.2 equiv, 32.6 mmol, 6.07 g) was
added. The solution was stirred for further 24 h at 60 °C.
After cooling to r.t., the mixture was washed with H2O, dried
with anhyd Na2SO4, and evaporated. The residue was
purified by column chromatography (CHCl3–MeOH, 30:1,
v/v). The N-protected phosphoglycinate was obtained as an
oil, 3.73 g, 51% yield. (c) Hoppe, D.; Beckmann, L. Liebigs
Ann. Chem. 1979, 2066.
C18H21N2O5S2P: C, 49.08; H, 4.91; N, 6.36; S, 14.56. Found:
C, 48.62; H, 4.93; N, 6.34; S, 14.45.
(21) The hydrolysis reactions were performed according to
literature procedure, see ref. 15a.
(17) General Procedure
To liquid NH3 (15 mL) at –78 °C a solution of nitroarene
(2.0 mmol) and 1b (269 mg, 1.0 mmol) was added followed
by dropwise addition of KOt-Bu in THF (1.05 mL, 1.00 M,
1.05 mmol) over 5 min. The reaction mixture was stirred at
this temperature for 30 min and then solid KMNO4 (156 mg,
1.0 mmol) was added. After 5 min reaction was quenched by
addition of NH4Cl (500 mg), and the mixture was left to
evaporation of NH3. The residue was treated with H2O (50
mL) and EtOAc (50 mL) and filtered through a pad of Celite.
The organic layer was separated, dried, and evaporated.
Products were isolated by column chromatography (EtOAc–
hexane).
Selected Analytical Data
Diethyl a-(5-Fluoro-2-nitrophenyl)phosphoglycinate (3c)
Oil. IR (film, CH2Cl2): nmax = 3250, 2987, 1689, 1589, 1532,
1351, 1236 cm–1. 1H NMR (400 MHz, CDCl3): d = 8.27 (s,
1 H), 8.00 (ddd, J = 0.4, 5.1, 9.0 Hz, 1 H), 7.64 (dt, J = 2.7,
9.5 Hz, 1 H), 7.13–7.09 (m, 1 H), 5.52 (d, J = 21.5 Hz),
4.26–4.00 (m, 4 H), 2.95 (br s, 1 H), 1.29 (t, J = 7.0 Hz, 3 H),
1.17 (t, J = 7.0 Hz, 3 H). 13C NMR (100 MHz, CDCl3):
d = 164.9 (d, J = 204 Hz), 160.9 (d, J = 7.4 Hz), 144.7 (dd,
J = 2.3, 5.0 Hz), 137.0 (d, J = 6.6 Hz), 127.9 (dd, J = 1.6, 7.8
Hz), 116.5 (dd, J = 2.4, 3.5 Hz), 115.4 (dd, J = 2.3, 18.6 Hz),
63.6 (d, J = 5.5 Hz), 63.5 (d, J = 5.5 Hz), 47.8 (d, J = 118
Hz), 16.3 (d, J = 2.5 Hz), 16.2 (d, J = 2.5 Hz). 31P NMR (162
MHz, CDCl3): d = 22.0. ESI-LRMS (+): 357 [M + Na]+.
Anal. Calcd for C12H16N2O6PF: C, 43.12; H, 4.83; N, 8.38.
Found: C, 43.16; H, 4.83; N, 8.30.
(18) Appel, R.; Loos, H.; Mayr, H. J. Am. Chem. Soc. 2009, 131,
704.
Synlett 2010, No. x, 1666–1668 © Thieme Stuttgart · New York