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cross-coupling. The formation of methyl-H-phosphinate esters is
especially noteworthy because it completely avoids hazardous
and expensive methyldichlorophosphine, and it can be used in tan-
dem reactions without intervening chromatographic purification.
The possibility to develop an asymmetric alkylation of alkyl phos-
phinates17 using a chiral DBU equivalent (amidines, guanidines,
etc.)18 is tantalizing.
5. Abbreviations:
DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene;
TBD = 1,5,7-
triazabicyclo[4.4.0]dec-5-ene; TMG = 1,1,3,3-tetramethylguanidine; DBN = 1,
5-diazabicyclo[4.3.0]non-5-ene, DABCO = 1,4-Diazabicyclo[2.2.2]octane.
6. (a) Deprèle, S.; Montchamp, J.-L. J. Organomet. Chem. 2002, 643–644, 154; (b)
Deprèle, S.; Montchamp, J.-L. J. Org. Chem. 2001, 66, 6745.
7. See for example: (a) Flynn, R. M.; Burton, D. J. J. Fluoresc. Chem. 2011, 132, 815;
(b) Georgiev, E.; Roundhill, D. M.; Troev, K. Inorg. Chem. 1965, 1992, 31; (c)
Atherton, F. R.; Todd, A. R. J. Chem. Soc. 1947, 674.
Acknowledgments
8. (a) Kinnear, A. M.; Perren, E. A. J. Chem. Soc. 1952, 3437; (b) Staendeke, H.;
Kleiner, H.-J. Angew. Chem., Int. Ed. 1973, 12, 877; (c) Petrov, K. A.; Bliznyuk, N.
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9. Bravo-Altamirano, K.; Huang, Z.; Montchamp, J.-L. Tetrahedron 2005, 61, 6315.
10. Bravo-Altamirano, K.; Abrunhosa-Thomas, I.; Montchamp, J.-L. J. Org. Chem.
2008, 73, 2292.
This material is based, in part, upon work supported by the Na-
tional Science Foundation under Grant No. 0953368 (CP). We also
thank the Robert A. Welch Foundation (Grant P-1666) for the
financial support of LG.
11. Queffélec, C.; Montchamp, J.-L. Org. Biomol. Chem. 2010, 8, 267.
12. Deal, E. L.; Petit, C.; Montchamp, J.-L. Org. Lett. 2011, 13, 3270.
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Fox, D. L.; Eubank, J. F.; Salvatore, R. N. Tetrahedron Lett. 2003, 44, 8617. and
references cited therein.
Supplementary data
Supplementary data (detailed experimental procedures, spectra
data, and NMR spectra) associated with this article can be found, in
15. The calculated pKa values in aqueous solution (SciFinder, Advance Chemistry
Development (ACD/Laboratories) Software V11.02, Ó 1994-2012 ACD/Labs) are
as follows:
References and notes
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4. Review: (a) Montchamp, J.-L. J. Organomet. Chem. 2005, 690, 2388;
Representative examples: (b) Fougère, C.; Guénin, E.; Hardouin, J.; Lecouvey,
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Docampo, R.; Rodriguez, J. B. J. Med. Chem. 2006, 49, 426; (f) Nan, F.; Bzdega, T.;
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In DMSO, the calculated pKa values for (PhO)2P(O)H and (MeO)2P(O)H are 9.0 and
18.4, respectively. See: Li, J.-N.; Liu, L.; Fu, Y.; Guo, Q.-X. Tetrahedron 2006, 62, 4453.
16. Lavén, G.; Stawinski, J. Synlett 2009, 225.
17. Bravo-Altamirano, K.; Coudray, L.; Deal, E. L.; Montchamp, J.-L. Org. Biomol.
Chem. 2010, 8, 5541.
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Chem. Eur. J. 2002, 8, 553.