D
S. Sano et al.
Letter
Synlett
References and Notes
1072, 963 cm–1. 1H NMR (500 MHz, CDCl3): δ = 4.51–4.42 (m, 4
H), 3.78 (s, 3 H), 3.17 (d, 2JH,P = 21.1 Hz, 2 H). 13C NMR (125 MHz,
2
1
(1) Edmonds, M.; Abell, A. The Wittig Reaction, In Modern Carbonyl
Olefination; Takeda, T., Ed.; Wiley-VCH: Weinheim, 2004.
(2) (a) Bisceglia, J. Á.; Orelli, L. A. Curr. Org. Chem. 2012, 16, 2206.
(b) Jasem, Y. A.; El-Esawi, R.; Thiemann, T. J. Chem. Res. 2014, 38,
453. (c) Bisceglia, J. Á.; Orelli, L. A. Curr. Org. Chem. 2015, 9, 744.
(d) Kobayashi, K.; Tanaka, K.; Kogen, H. Tetrahedron Lett. 2018,
59, 568.
(3) DeHoff, B.; Roy, M.-N. Methyl Bis(2,2,2-trifluoroethoxy)phosphi-
nylacetate, In e-EROS Encyclopedia of Reagents for Organic Syn-
thesis; Wiley: New York, 2012.
(4) (a) Siau, W.-Y.; Zhang, Y.; Zhao, Y. Top. Curr. Chem. 2012, 327,
33. (b) Li, J. J. Still–Gennari Phosphonate Reaction, In Name Reac-
tions: A Collection of Detailed Mechanisms and Synthetic Applica-
tions, 5th ed.; Springer: Berlin, Heidelberg, 2014.
(5) Still, W. C.; Gennari, C. Tetrahedron Lett. 1983, 24, 4405.
(6) Messik, F.; Oberthür, M. Synthesis 2013, 45, 167.
CDCl3): δ = 165.2 (d, JC,P = 4.5 Hz), 122.5 (qd, JC,F = 277.1 Hz,
3JC,P = 8.2 Hz), 62.7 (qd, 2JC,F = 38.2 Hz, 2JC,P = 5.5 Hz), 53.1, 33.8 (d,
1JC,P
= 145.1 Hz). HRMS (ESI): m/z [M +
Na]+ calcd for
C7H9F6O5PNa: 340.9990; found: 340.9982. Anal. Calcd for
C7H9F6O5P: C, 26.43; H, 2.85. Found: C, 26.28; H, 2.89.
(14) Methyl 2-[Bis(phenylthio)phosphoryl]acetate (7f)
Colorless oil; yield 79.5 mg (85%). IR (neat): 3059, 2952, 1737,
1473, 1439, 1268, 1220, 1107, 1023, 1002 cm–1 1H NMR (500
.
MHz, CDCl3): δ = 7.63–7.59 (m, 4 H), 7.45–7.36 (m, 6 H), 3,77 (s,
3 H), 3.30 (d, 2JH,P = 16.2 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ =
2
3
5
165.1 (d, JC,P = 4.6 Hz), 136.0 (d, JC,P = 4.4 Hz), 129.8 (d, JC,P
=
2.8 Hz), 129.5 (d, 4JC,P = 2.1 Hz), 125.3 (d, 2JC,P = 6.5 Hz), 52.8, 42.6
(d, JC,P = 61.4 Hz). HRMS (ESI): m/z [M + Na]+ calcd for
1
C
C
15H15O3PS2Na: 361.0098; found: 361.0069. Anal. Calcd for
15H15O3PS2: C, 53.24; H, 4.47. Found: C, 52.96; H, 4.67.
Methyl 2-[Bis(phenylamino)phosphoryl]acetate (7g)
(7) (a) Sano, S.; Sumiyoshi, H.; Handa, A.; Tokizane, R.; Nakao, M.
Tetrahedron Lett. 2015, 56, 4686. (b) Nakao, M.; Tanaka, K.;
Kitaike, S.; Sano, S. Synthesis 2017, 49, 3654.
Pale yellow columns (CHCl3/n-hexane); mp 115.0–116.0 °C;
yield 71.9 mg (86%). IR (KBr): 3330, 3185, 1731, 1602, 1502,
1
1434, 1397, 1282, 1268, 1242, 1207, 1181, 1106 cm–1. H NMR
(8) Mundy, B. P.; Ellerd, M. G.; Favaloro, F. G. Jr. In Name Reactions
and Reagents in Organic Synthesis, 2nd ed.; John Wiley and Sons:
Hoboken, NJ, 2005, 268.
(500 MHz, CDCl3): δ = 7.23–7.17 (m, 4 H), 7.16–7.12 (m, 4 H),
2
6.99–6.93 (m, 2 H), 6.25 (br s, 2 H), 3.65 (s, 3 H), 3.17 (d, JH,P
=
19.3 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 168.4 (d, 2JC,P = 4.5
2
(9) (a) Garegg, P. J.; Samuelsson, B. J. Chem. Soc., Chem. Commun.
1979, 978. (b) Garegg, P. J.; Samuelsson, B. Synthesis 1979, 469.
(c) Garegg, P. J.; Samuelsson, B. Synthesis 1979, 813. (d) Garegg,
P. J.; Samuelsson, B. J. Chem. Soc., Perkin Trans. 1 1980, 2866.
(e) Classon, B.; Garegg, P. J.; Samuelsson, B. Can. J. Chem. 1981,
59, 339. (f) Garegg, P. J.; Johansson, R.; Ortega, C.; Samuelsson, B.
J. Chem. Soc., Perkin Trans. 1 1982, 681. (g) Garegg, P. J.;
Johansson, R.; Samuelsson, B. Synthesis 1984, 168.
(10) Morcillo, S. P.; de Cienfuegos, L. Á.; Mota, A. J.; Justicia, J.;
Robles, R. J. Org. Chem. 2011, 76, 2277.
(11) Purohit, A. K.; Pardasani, D.; Tak, V.; Kumar, A.; Jain, R.; Dubey,
D. K. Tetrahedron Lett. 2012, 53, 3795.
(12) (a) Grison, C.; Coutrot, P.; Comoy, C.; Balas, L.; Joliez, S.;
Lavecchia, G.; Oliger, P.; Penverne, B.; Serre, V.; Hervé, G. Eur. J.
Med. Chem. 2004, 39, 333. (b) Gao, J.; Ju, K.-S.; Yu, X.; Velásquez,
J. E.; Mukherjee, S.; Lee, J.; Zhao, C.; Evans, B. S.; Doroghazi, J. R.;
Metcalf, W. W.; van der Donk, W. A. Angew. Chem. Int. Ed. 2014,
53, 1334.
Hz), 139.5, 129.3, 122.4, 118.9 (d, JC,P = 6.4 Hz), 52.8, 35.9 (d,
1JC,P
= 103.8 Hz). HRMS (ESI): m/z [M +
Na]+ calcd for
C
C
15H17N2O3PNa: 327.0874; found: 327.0858. Anal. Calcd for
15H17N2O3P: C, 59.21; H, 5.63; N, 9.21. Found: C, 59.18; H, 5.66;
N, 8.98.
(15) (a) Ando, K. J. Org. Chem. 1997, 62, 1934. (b) Ando, K. J. Org.
Chem. 1998, 63, 8411. (c) Ando, K. J. Org. Chem. 1999, 64, 6815.
(d) Ando, K. J. Org. Chem. 1999, 64, 8406.
(16) Spinelli, D.; Petrillo, G.; Pettigrew, J. D.; Honson, N. S. Bis(2,2,2-
trifluoroethyl)bromophosphonoacetate, In e-EROS Encyclopedia
of Reagents for Organic Synthesis; Wiley: New York, 2016.
(17) (a) Tago, K.; Kogen, H. Org. Lett. 2000, 2, 1975. (b) Tago, K.;
Kogen, H. Tetrahedron 2000, 56, 8825. (c) Olpp, T.; Brückner, R.
Synthesis 2004, 2135. (d) Nakata, A.; Kobayashi, K.; Kogen, H.
Chem. Pharm. Bull. 2013, 61, 108.
(18) Jiang, J. Triethyl 2-Fluoro-2-phosphonoacetate, In e-EROS Ency-
clopedia of Reagents for Organic Synthesis; Wiley: New York,
2006.
(13) Preparation of Methyl Bis(2,2,2-trifluoroethyl)phosphono-
(19) (a) Elkik, E.; Imbeaux, M. Synthesis 1989, 861. (b) Patois, C.;
Savignac, P. Synth. Commun. 1994, 24, 1317. (c) Davis, F. A.; Han,
W.; Murphy, C. K. J. Org. Chem. 1995, 60, 4730. (d) Zhang, X.;
Qiu, W.; Burton, D. J. Tetrahedron Lett. 1999, 40, 2681.
(e) Marma, M. S.; Khawli, L. A.; Harutunian, V.; Kashemirov, B.
A.; McKenna, C. E. J. Fluorine Chem. 2005, 126, 1467.
(20) Ethyl 2-[Bis(2,2,2-trifluoroethoxy)phosphoryl]-2-fluoroace-
tate (10)
acetate (Still–Gennari Reagent, 1)5,6
TMSBr (90 μL, 0.691 mmol) was added at r.t. to a solution of
trimethyl phosphonoacetate (2; 50.3 mg, 0.276 mmol) in anhy-
drous CH2Cl2 (0.55 mL). After stirring at r.t. for 5 h under argon,
evaporation of the reaction mixture in vacuo gave methyl 2-
{bis[(trimethylsilyl)oxy]phosphoryl}acetate (4), which was
used without further purification. Ph3P (181 mg, 0.691 mmol)
and I2 (175 mg, 0.691 mmol) were added to a solution of 4 in
anhydrous CHCl3 (1.8 mL) at r.t. under argon. After stirring at r.t.
for 15 min under argon, imidazole (188 mg, 2.76 mmol) was
added. The reaction mixture was stirred for 15 min at r.t. and
then for 30 min at 50 °C. Afterwards, 2,2,2-trifluoroethanol (79
μL, 1.10 mmol) was added, and the reaction mixture was stirred
at 60 °C for 5 h. After filtration of the reaction mixture, the fil-
trate was evaporated in vacuo to give a crude product 1, which
was purified by silica gel [Silica Gel PSQ 60B (Fuji Silysia Chemi-
cal)] column chromatography [n-hexane–EtOAc (2:1)] to afford
1 (82.3 mg, 94%) as a colorless oil. IR (neat): 1747, 1265, 1174,
Colorless oil; yield 46.1 mg (49%). IR (neat): 2983, 2947, 1770,
1456, 1420, 1374, 1271, 1174, 1068, 1021, 963 cm–1 1H NMR
.
(500 MHz, CDCl3): δ = 5.34 (dd, 2JH,F = 46.4 Hz, 2JH,P = 12.8 Hz, 1
H), 4.60–4.43 (m, 4 H), 4.38 (q, J = 7.1 Hz, 2 H), 1.36 (t, J = 7.2 Hz,
2
3 H). 13C NMR (125 MHz, CDCl3): δ = 163.4 (dd, JC,F = 21.8 Hz,
2JC,P = 1.9 Hz), 122.1 (qdd, 1JC,F = 277.8 Hz, 3JC,P = 8.0 Hz, 5JC,F = 5.6
1
1
2
Hz), 84.3 (dd, JC,F = 199.7 Hz, JC,P = 168.0 Hz), 63.5 (qd, JC,F
=
38.8 Hz, JC,P = 5.9 Hz), 63.3, 13.9. HRMS (ESI): m/z [M + Na]+
calcd for C8H10F7O5PNa: 373.0052; found: 373.0046. Anal. Calcd
for C8H10F7O5P: C, 27.44; H, 2.88. Found: C, 27.49; H, 3.10.
2
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–D