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S. Guo et al.
Letter
Synlett
which activated the amino group of amino-2-en-1-ones to
deliver the monophosphorylated products.8 Then, Lewis
acid activated the carbonyl group, and the nucleophile of
trialkyl phosphite added to the alkene to form A. With the
assistance of H2O, the bisphosphorylated product was af-
forded.
In summary, we have developed an iron-catalyzed bis-
phosphorylation of amino-2-en-1-ones and trialkyl phos-
phites to prepare 1,3-diphosphoric acid derivatives under
mild conditions.11–13 This reaction is an effective supple-
ment of the previous work to forge the alkyl 1,3-diphos-
phorus compounds. Additionally, unsymmetrical 1,3-di-
phosphonate esters were obtained by a sequential addition
according to this strategy.
L.-B. Green Chem. 2018, 20, 3408. (g) Fernández-Valle, M. E.;
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D. S.; Golen, J. A.; Rheingold, A. L. J. Org. Chem. 2018, 83, 3928.
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2009, 11, 2543.
Funding Information
We thank the National Natural Science Foundation of China
(21861024, 21571094, 21761021) for financial support.
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Supporting Information
(8) Huang, L.; Zhang, Z.; Jie, K.; Wang, Y.; Fu, Z.; Guo, S.; Cai, H. Org.
Chem. Front. 2018, 5, 3548.
Supporting information for this article is available online at
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(9) (a) Liu, L.; Wu, Y.; Wang, Z.; Zhu, J.; Zhao, Y. J. Org. Chem. 2014,
79, 6816. (b) Lygo, B.; Beynon, C.; Lumley, C.; Mcleod, M. C.;
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References and Note
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(11) 2-[(Diethylamino)methyl]-1-phenylprop-2-en-1-one (1a)
Ketone 1 (1 mmol) was mixed with silica gel (2.0 g) in a mortar.
Then formaldehyde (0.18 g, 3 mmol, 37% in H2O) and dialkyl-
amine (2 mmol) were added and mixed. The mixture was
placed into a flask with a cap and stirred for 5–7 h at room tem-
perature. Then diethyl ether (20 mL) was added. After filtration
and the removal of the solvent at the reduced pressure, the
product was isolated. Further purification of the crude reaction
mixture on silica gel column gave the pure product.
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(12) General Procedure for 3a
To a 50 mL Schlenk tube with a stir bar added allylamine deriva-
tives 1a (81.9 mg, 0.3 mmol), triethyl phosphite (149.5 mg, 3
equiv), Fe(NO3)3·9H2O (20 mol%), and DCE (2 mL), the mixture
was stirred at 100 °C for 5 h and monitored by TLC. The solution
was then evaporated under vacuum. The crude reaction
mixture was purified by column chromatography on silica gel
(pure EtOAc) to get product 3a.1H NMR (400 MHz, CDCl3): =
8.12 (d, J = 7.4 Hz, 2 H), 7.58 (t, J = 7.1 Hz, 1 H), 7.51 (t, J = 7.4 Hz,
2 H), 4.34 (ddd, J = 20.5, 13.9, 6.6 Hz, 1 H), 4.13–3.91 (m, 8 H),
2.44–2.32 (m, 2 H), 2.14–2.01 (m, 2 H), 1.24 (t, J = 7.0 Hz, 6 H),
1.14 (t, J = 7.0 Hz, 6 H) ppm.13C NMR (101 MHz, CDCl3): =
199.77, 199.68, 199.59, 135.05, 133.61, 128.92, 128.88, 77.32,
77.00, 76.68, 62.56, 62.49, 62.35, 62.29, 34.46, 34.43, 34.41,
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© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–E