ORGANIC
LETTERS
2006
Vol. 8, No. 18
4169-4171
Palladium-Catalyzed Dehydrative
Allylation of Hypophosphorous Acid
with Allylic Alcohols
Karla Bravo-Altamirano and Jean-Luc Montchamp*
Department of Chemistry, Box 298860, Texas Christian UniVersity,
Fort Worth, Texas 76129
Received July 24, 2006
ABSTRACT
A novel palladium-catalyzed allylation of H3PO2 with allylic alcohols is described. The phosphorus−carbon bond-forming reaction produces
allylic-H-phosphinic acids and water, in the absence of additives. Primary H-phosphinic acids are obtained in excellent yields, whereas secondary
H-phosphinic acids react sluggishly. A reusable polymer-supported catalyst is also described. The reaction provides an environmentally
sound approach to H-phosphinic acids.
Palladium-catalyzed allylations have become well-established
and reliable methods for forming C-O, C-N, and C-C
bonds but are much less common for C-P bond formation.1
Commonly used electrophiles are halides or esters (acetate,
carbonate, phosphate) derived from an allylic alcohol. More
recently, research has focused on the development of catalytic
allylations which use allylic alcohols directly.2,3 The obvious
advantages are the ready availability of the starting materials
and a more atom-economical and environmentally benign
approach because water is the byproduct (eq 1).
drophosphinylation of alkenes and alkynes.6 Herein, we
report the palladium-catalyzed allylation of H3PO2 with
(2) Reviews: (a) Muzart, J. Tetrahedron 2005, 61, 4179. (b) Tamaru,
Y. Eur. J. Org. Chem. 2005, 2647. For allylation with allylic alcohols in
the presence of additives, see, for example: (c) Yang, S.-C.; Hsu, Y.-C.;
Gan, K.-H. Tetrahedron 2006, 62, 3949. (d) Zhu, S.-F.; Yang, Y.; Wang,
L.-X.; Liu, B.; Zhou, Q.-L. Org. Lett. 2005, 7, 2333. (e) Fontana, G.;
Lubineau, A.; Scherrmann, M.-C. Org. Biomol. Chem. 2005, 3, 1375. (f)
Manabe, K.; Kobayashi, S. Org. Lett. 2003, 5, 3241. (g) Ozawa, F.;
Okamoto, H.; Kawagishi, S.; Yamamoto, S.; Minami, T.; Yoshifuji, M. J.
Am. Chem. Soc. 2002, 124, 10968. (h) Yang, S.-C.; Tsai, Y.-C. Organo-
metallics 2001, 20, 763. (i) Chandrasekhar, S.; Jagadeshwar, V.; Saritha,
B.; Narsihmulu, C. J. Org. Chem. 2005, 70, 6506. (j) Takahara, J. P.;
Masuyama, Y.; Kurusu, Y. J. Am. Chem. Soc. 1992, 114, 2577.
(3) Examples of direct allylation without additives: (a) Olsson, V. J.;
Sebelius, S.; Selander, N.; Szabo, K. J. J. Am. Chem. Soc. 2006, 128, 4588.
(b) Kayaki, Y.; Koda, T.; Ikariya, T. Eur. J. Org. Chem. 2004, 4989. (c)
Kayaki, Y.; Koda, T.; Ikariya, T. J. Org. Chem. 2004, 69, 2595. (d) Trost,
B. M.; Spagnol, M. D. J. Chem. Soc., Perkin Trans. 1 1995, 2083. (e)
Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535.
(4) Reviews: (a) Montchamp, J.-L. J. Organomet. Chem. 2005, 690,
2388. (b) Montchamp, J.-L. Spec. Chem. Mag. 2006, 26, 44.
(5) (a) Bravo-Altamirano, K.; Huang, Z.; Montchamp, J.-L. Tetrahedron
2005, 61, 6315. (b) Huang, Z.; Bravo-Altamirano, K.; Montchamp, J.-L.
C. R. Chimie 2004, 7, 763. (c) Dumond, Y. R.; Montchamp, J.-L. J.
Organomet. Chem. 2002, 653, 252. (d) Montchamp, J.-L.; Dumond, Y. R.
J. Am. Chem. Soc. 2001, 123, 510.
(6) (a) Ribie`re, P.; Bravo-Altamirano, K.; Antczak, M.; Hawkins, J. D.;
Montchamp, J.-L. J. Org. Chem. 2005, 70, 4064. (b) Depre`le, S.;
Montchamp, J.-L. J. Am. Chem. Soc. 2002, 124, 9386.
As part of our program to develop phosphorus-carbon
bond-forming reactions using hypophosphorous acid (H3PO2)
and its derivatives,4 we have reported the palladium-catalyzed
cross-coupling of aryl and alkenyl electrophiles5 and the hy-
(1) For metal-catalyzed allylation with P-C bond formation: (a) Lu,
X.; Zhu, J. Synthesis 1986, 563. (b) Lu, X.; Zhu, J.; Huang, J.; Tao, X. J.
Mol. Catal. 1987, 41, 235. (c) Lu, X.; Tao, X.; Zhu, J.; Sun, X.; Xu, J.
Synthesis 1989, 848. (d) Lu, X.; Zhu, J. J. Organomet. Chem. 1986, 304,
239.
10.1021/ol061828e CCC: $33.50
© 2006 American Chemical Society
Published on Web 08/10/2006