ORGANIC
LETTERS
2011
Vol. 13, No. 12
3134–3137
Synthesis of Z-Alkenyl Phosphorus
Compounds through Hydroalumination
and Carbocupration of Alkynyl Precursors
ꢀ
Stephanie Ortial and Jean-Luc Montchamp*
Department of Chemistry, Box 298860, Texas Christian University, Fort Worth,
Texas 76129, United States
Received April 18, 2011
ABSTRACT
The stereocontrolled synthesis of Z-alkenylphosphineÀborane complexes is easily accomplished via the hydroalumination or carbocupration of
alkynyl precursors. Z/E ratios are generally higher than 95/5. These reactions are stereocomplementary to our olefination approach.
Organophosphorus compounds are key synthetic inter-
mediates, especially for the preparation of phosphine
ligands. Among them, conjugated alkenyl phosphorus
derivatives are of particular interest since the carbonÀ
carbon double bond can be functionalized further. A
variety of methods have been reported for the preparation
of alkenyl phosphines, their borane complexes, and their
oxides.1 These include metal-catalyzed cross-coupling,
olefin metathesis, and hydrophosphination and related
reactions. The wealth of literature references is an indica-
tion of the intense activity in this field.1 Similarly, a
plethora of methods exists to prepare variously substituted
alkenyl phosphonates.2
Recently, we reported a simple and general method to
access a variety of alkenylphosphorus compounds via car-
bonyl olefination with mixed 1,1-bisphosphorus reagents.3
(1) Selected reviews. Alk-1-enylphosphines: (a) Gaumont, A. C.;
Gulea, M. Science of Synthesis, Houben Weyl Methods of Molecular
Transformations; Georg Thieme Verlag KG: Stuttgart, 2007; Vol. 33, pp
711À724. (b) Alk-1-enyl phosphorus compounds: Gaumont, A. C.;
Gulea, M. Science of Synthesis, Houben Weyl Methods of Molecular
Transformations; Georg Thieme Verlag KG: Stuttgart, 2007; Vol. 33,
pp 665À694. (c) Alk-1-enylphosphine oxides and derivatives: Gaumont,
A. C.; Gulea, M. Science of Synthesis, Houben Weyl Methods of
Molecular Transformations; Georg Thieme Verlag KG: Stuttgart, 2007;
Vol. 33, pp 701À710. (d) Alk-1-enylphosphinic acids and derivatives:
Gaumont, A. C.; Gulea, M. Science of Synthesis, Houben Weyl Methods
of Molecular Transformations; Georg Thieme Verlag KG: Stuttgart, 2007;
Vol. 33, pp 695À700. (e) Delacroix, O.; Gaumont, A.-C. Curr. Org.
Chem. 2005, 9, 1851. (f) Gilheany, D. G.; Mitchell, C. M. In Chemistry of
Organophosphorus Compounds; Hartley, F. R., Ed.; Wiley: Chichester,
1990; Vol. 1, pp 151À190; (g) Alonso, F.; Beletskaya, I. P.; Yus, M.
Chem. Rev. 2004, 104, 3079. (h) Promonenkov, V. K.; Ivin, S. Z. Russ.
Chem. Rev. 1968, 37, 670. (i) Coudray, L.; Montchamp, J.-L. Eur. J. Org.
Chem. 2008, 3601. (j) Glueck, D. S. Top. Organomet. Chem. 2010, 31, 65.
(k) Tappe, F. M. J.; Trepohl, V. T.; Oestreich, M. Synthesis 2010, 3037.
Selected representative examples: (l) Gonzalez-Nogal, A. M.; Cuadrado,
P.; Sarmentero, M. A. Tetrahedron 2010, 66, 9610. (m) Kondoh, A.;
Yorimitsu, H.; Oshima, K. Bull. Chem. Soc. Jpn. 2008, 81, 502. (n)
Dunne, K. S.; Lee, S. E.; Gouverneur, V. J. Organomet. Chem. 2006, 691,
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Busacca, C. A.; Farber, E.; De Young, J.; Campbell, S.; Gonnella, N. C.;
Grinberg, N.; Haddad, N.; Lee, H.; Ma, S.; Reeves, D.; Shen, S.;
Senanayake, C. H. Org. Lett. 2009, 11, 5594.
(2) Representative examples: (a) Dembitsky, V. M.; Al Quntar,
A. A. A.; Haj-Yehia, A.; Srebnik, M. Mini-Rev. Org. Chem. 2005, 2,
91. (b) Minami, T.; Motoyoshiya, J. Synthesis 1992, 333. (c) Kabalka,
G. W.; Guchhait, S. K. Org. Lett. 2003, 5, 729. (d) Yamashita, M.;
Tamada, Y.; Iida, A.; Oshikawa, T. Synthesis 1990, 420. (e) Chatterjee,
A. K.; Choi, T.-L.; Grubbs, R. H. Synlett 2001, 1034. (f) Janecki, T.;
Kedzia, J.; Wasek, T. Synthesis 2009, 1227. (g) Al Quntar, A. A. A.;
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X.-P.; Wang, D.-Y.; Huang, J.-D.; Yu, S.-B.; Deng, J.; Zheng, Z. Adv.
Synth. Catal. 2008, 350, 1979. (i) Rabasso, N.; Fadel, A. Tetrahedron
Lett. 2010, 51, 60. (j) Cullen, S. C.; Rovis, T. Org. Lett. 2008, 10, 3141. (k)
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Sulzer-Mosse, S.; Tissot, M.; Alexakis, A. Org. Lett. 2007, 9, 3749. (l)
Ettari, R.; Nizi, E.; Di Francesco, M. E.; Micale, N.; Grasso, S.;
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Zappala, M.; Vicik, R.; Schirmeister, T. Chem. Med. Chem. 2008, 3,
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1030. (m) Delomenede, M.; Bedos-Belval, F.; Duran, H.; Vindis, C.;
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Baltas, M.; Negre-Salvayre, A. J. Med. Chem. 2008, 51, 3171. (n)
Krawczyk, H.; Albrecht, L. Synthesis 2005, 2887. (o) Quntar,
A. A. A.; Melman, A.; Srebnik, M. Synlett 2002, 61. (p) Chakravarty,
M.; Swamy, K. C. K. Synthesis 2007, 3171. (q) Thielges, S.; Bisseret, P.;
Eustache, J. Org. Lett. 2005, 7, 681. (r) Savignac, P.; Iorga, B. Modern
Phosphonate Chemistry; CRC Press: Boca Raton, 2003.
(3) Ortial, S.; Thompson, D. A.; Montchamp, J.-L. J. Org. Chem.
2010, 75, 8166.
r
10.1021/ol2010374
Published on Web 05/19/2011
2011 American Chemical Society