PAPER
Synthesis of Novel a-Aminophosphonates
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1JCP = 145 Hz, CHPO(OEt)2], 61.82 (OCH2CH3), 61.88
(OCH2CH3), 105.40 (=CH2), 127.07 (CHphenyl), 128.30 (2 CHphenyl),
128.38 (2 CHphenyl), 140.09 (Cphenyl), 145.89 (C=CH2).
References
(1) For some recent reviews, see: (a) Cativiela, C.; Diaz-de-
Villegas, M. D. Tetrahedron: Asymmetry 2000, 11, 645.
(b) Brandi, A.; Goti, A. Chem. Rev. 1998, 98, 589.
(c) Salaün, J. Top. Curr. Chem. 2000, 207, 1. (d) Komarov,
V.; Grigorenko, A. O.; Turov, A. V.; Khilya, V. P. Russ.
Chem. Rev. 2004, 73, 785; Chem. Abstr. 2005, 143, 78445.
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Meijere, A.; Ernst, K.; Zuck, B.; Brandl, M.; Kozhushkov, S.
I.; Tamm, M.; Yufit, D. S.; Howard, J. A. K.; Labahn, T.
Eur. J. Org. Chem. 1999, 3105. (c) Pellicciari, R.;
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31P NMR (CDCl3): d = 27.81.
Anal. Calcd for C17H26NO3P: C, 63.14; H, 8.10; N, 4.33. Found: C,
63.20; H, 8.18; N, 4.29.
Diethyl (Benzylamino)[4-(ethoxycarbonyl)spiro[2.2]pent-1-
yl]methylphosphonate (8e)
Yield: 66%; mixture of diastereomers (A/B/C/D/E/F/G/H =
10:8:6:5:3:2:1:1).15
1H NMR (CDCl3): d (8 diastereomers) = 0.50–1.31 (m, 4 H, 2 cPr-
CH2 ), 1.03–1.22 (m, 9 H, 3 OCH2CH3), 1.32–1.50 (m, 1 H, cPr-CH
), 1.72–1.82 (m, 1 H, cPr-CH), 2.08 (m, 1 H, NHCH2), 2.25–2.80
[m, 1 H, CHPO(OEt)2], 3.64–3.87 (m, 2 H, CH2Ph), 3.88–4.15 (m,
6 H, 3 OCH2CH3), 7.07–7.27 (m, 5 H, Ph).
13C NMR (CDCl3): d (isomer A) = 12.06 (cPr-CH2), 12.27 (cPr-
CH2), 14.15 (CO2CH2CH3), 16.36 [2 PO(OCH2CH3)2], 19.00 (cPr-
CH), 20.09 (cPr-CH), 23.02 (Cspiro), 52.90 (CH2NH), 57.92 [d,
1JCP = 168 Hz, CHPO(OEt)2], 60.01 (CO2CH2CH3), 61.96
[PO(OCH2CH3)2], 62.03 [PO(OCH2CH3)2], 126.90 (CHphenyl),
128.05 (4 CHphenyl), 139.58 (Cphenyl), 173.39 [CO2(CH2CH3)].
13C NMR (CDCl3): d (isomer B) = 12.92 (cPr-CH2), 13.00 (cPr-
CH2), 14.11 (CO2CH2CH3), 16.42 [2 PO(OCH2CH3)2], 17.77 (cPr-
CH), 19.64 (cPr-CH), 22.69 (Cspiro), 51.90 (CH2NH), 56.99 [d,
1JCP = 157 Hz, CHPO(OEt)2], 60.33 (CO2CH2CH3), 61.75
[PO(OCH2CH3)2], 61.82 [PO(OCH2CH3)2], 126.68 (CHphenyl),
128.16 (4 CHphenyl), 139.96 (Cphenyl), 172.94 (CO2CH2CH3).
13C NMR (CDCl3): d (isomer C) = 10.91 (cPr-CH2), 11.06 (cPr-
CH2), 14.04 (CO2CH2CH3), 16.30 [2 PO(OCH2CH3)2], 18.70 (cPr-
CH), 20.04 (cPr-CH), 23.96 (Cspiro), 51.97 (CH2NH), 56.54 [d,
1JCP = 152 Hz, CHPO(OEt)2], 59.97 (CO2CH2CH3), 62.06
[PO(OCH2CH3)2], 62.08 [PO(OCH2CH3)2], 126.85 (CHphenyl),
128.00 (4 CHphenyl), 139.65 (Cphenyl), 172.83 (CO2CH2CH3).
(f) Jimenez, A. I.; Lopez, P.; Cativiela, C. Chirality 2005, 17,
22.
(3) (a) Dhawan, B.; Redmore, D. Phosphorus Sulfur Relat.
Elem. 1987, 32, 119. (b) De Lombaert, S.; Blanchard, L.;
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Chem. Lett. 1995, 5, 145. (c) Burgess, K.; Kwok-Kan, H.;
Destradi, M. S. Synlett 1994, 575. (d) Kafarski, B.; Lejczak,
B. Phosphorus, Sulfur Silicon Relat. Elem. 1991, 63, 193.
(e) Fields, S. C. Tetrahedron 1999, 55, 12237.
(f) Kleszczynska, H.; Sarapuk, J. Cell. Mol. Biol. Lett. 2001,
6, 83. (g) Hiratake, J.; Oda, J. Biosci. Biotechnol. Biochem.
1997, 61, 211.
(4) (a) Averina, E. B.; Yashin, N. V.; Grishin, Yu. K.;
Kuznetsova, T. S.; Zefirov, N. S. Synthesis 2006, 880.
(b) Yashin, N. V.; Averina, E. B.; Grishin, Yu. K.;
Kuznetsova, T. S.; Zefirov, N. S. Synthesis 2006, 279.
(c) Averina, E. B.; Yashin, N. V.; Shvorina, E. B.; Grishin,
Yu. K.; Kuznetsova, T. S. Vestn. Mosk. Univ., Ser. 2: Khim.
2005, 46, 314; Chem. Abstr. 2006, 145, 145989. (d)Yashin,
N. V.; Averina, E. B.; Gerdov, S. M.; Kuznetsova, T. S.;
Zefirov, N. S. Tetrahedron Lett. 2003, 44, 8241.
13C NMR (CDCl3): d (isomer D) = 9.52 (cPr-CH2), 9.55 (cPr-CH2),
14.09 (CO2CH2CH3), 16.46 [2 PO(OCH2CH3)2], 18.33 (cPr-CH),
18.42 (cPr-CH), 24.17 (Cspiro), 51.83 (CH2NH), 52.28 [d, 1JCP = 157
Hz, CHPO(OEt)2], 59.94 (CO2CH2CH3), 62.25 [PO(OCH2CH3)2],
62.33 [PO(OCH2CH3)2], 126.95 (CHphenyl), 128.55 (4 CHphenyl),
139.82 (Cphenyl), 173.20 (CO2CH2CH3).
(e) Averina, E. B.; Yashin, N. V.; Kuznetsova, T. S.;
Zefirov, N. S. Vestn. Mosk. Univ., Ser. 2: Khim. 2002, 43,
246; Chem. Abstr.; 2002, 138: 254854.
(5) (a) Erion, M. D.; Walsh, C. T. Biochemistry 1987, 26, 3417.
(b) Fadel, A. J. Org. Chem. 1999, 64, 4953.
(6) (a) Tesson, N.; Dorigneux, B.; Fadel, A. Tetrahedron:
Asymmetry 2002, 13, 2267. (b) Fadel, A.; Tesson, N.
Tetrahedron: Asymmetry 2000, 11, 2023. (c) Groth, U.;
Lehmann, L.; Richter, L.; Schöllkopf, U. Liebigs Ann.
Chem. 1993, 427. (d) Hercouet, A.; Le Corre, M.; Carboni,
B. Tetrahedron Lett. 2000, 41, 197. (e) Yamazaki, S.;
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Chem. 1998, 63, 5919.
(7) (a) Demir, A. S.; Tanyeli, C.; Sesenoglu, O.; Demic, S.
Tetrahedron Lett. 1996, 37, 407. (b) Hannour, S.;
Roumestant, M.-L.; Viallefont, P.; Riche, C.; Martinez, J.;
El-Hallaoui, A.; Ouazzani, F. Tetrahedron: Asymmetry
1998, 9, 2329.
13C NMR (CDCl3): d (isomer E) = 9.39 (cPr-CH2), 9.42 (cPr-CH2),
14.00 (CO2CH2CH3), 16.25 [2 PO(OCH2CH3)2], 18.52 (cPr-CH),
18.54 (cPr-CH), 23.19 (Cspiro), 51.76 (CH2NH), 56.69 [d, 1JCP = 150
Hz, CHPO(OEt)2], 60.28 (CO2CH2CH3), 61.88 [PO(OCH2CH3)2],
61.92 [PO(OCH2CH3)2], 126.63 (CHphenyl), 128.11 (4 CHphenyl),
140.28 (Cphenyl), 173.35 (CO2CH2CH3).
31P NMR (CDCl3): d (isomer A) = 26.08.
31P NMR (CDCl3): d (isomer B) = 26.11.
31P NMR (CDCl3): d (isomer C) = 26.59.
31P NMR (CDCl3): d (isomer D) = 26.16.
31P NMR (CDCl3): d (isomer E) = 26.79.
(8) For review see: Cherkasov, R. A.; Galkin, V. I. Russ. Chem.
Rev. 1998, 67, 857; Chem. Abstr. 1999, 130, 139371.
(9) Kabachnik, M. I.; Medved, T. Y. Dokl. Akad. Nauk SSSR
1952, 689; Chem. Abstr. 1953, 47, 2724b.
HRMS (MALDI-TOF): m/z [M + 1]+ calcd for C20H31NO5P:
396.1940; found: 396.1977.
(10) Kabachnik, M. M.; Ternovskaya, T. M.; Zobnina, E. V.;
Beletskaya, I. P. Russ. J. Org. Chem. (Engl. Transl.) 2002,
38, 480; Chem. Abstr. 2002, 137, 370153.
(11) (a) Matveeva, E. D.; Podrugina, T. A.; Tishkovskaya, E. V.;
Zefirov, N. S. Synlett 2003, 2321. (b) Matveeva, E. D.;
Zefirov, N. S. Russ. J. Org. Chem. (Engl. Transl.) 2006, 42,
1237. (c) Matveeva, E. D.; Podrugina, T. A.; Prisyajnoy, M.
V.; Zefirov, N. S. Russ. Chem. Bull. 2006, 55, 1209.
Acknowledgment
This work was supported by the Russian Foundation of Basic Rese-
arch (Project 05-03-32906-a), Division of Chemistry and Materials
Science RAS (Program I.1), Ministry of Education and Science of
Russian Federation (Project 2552.2006.3).
Synthesis 2008, No. 3, 464–468 © Thieme Stuttgart · New York