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Brandsma, L.; Vasilevsky, S. F.; Verkruijsse, H. D.
Application of Transition Metal Catalysts in Organic
Synthesis; Springer: Berlin, Heidelberg, New York, 1999.
2. Gilheany, D. G.; Mitchell, C. M. In The Chemistry of
Organophosphorus Compounds; Hartley, F. R., Ed.; John
Wiley and Sons: Chichester, 1990; Vol. 1, pp 151–190.
3. Fritz, G.; Scheer, P. Chem. Rev. 2000, 100, 3341–3401.
4. (a) Bordachev, A. A.; Kagachnik, M. M.; Novikova, Z. S.;
Beletskaya, I. P. Izv. Akad. Nauk. Ser. Khim. 1994, 4, 754–
756; (b) Kolodiazhnyi, O. I.; Guliaiko, I. V.; Kolodiazhna,
A. O. Tetrahedron Lett. 2004, 45, 6955–6957.
CO2Et
1d
+
Ph2P
TASF
DMF
t
Ph2PSiMe2 Bu
2
CO2Et
Ph2P
OH
Ph
CO2Et
7 97%
PhCHO
rt, 3 h
Ph2P
(d.r. = 3 : 2)
5. Kunzek, H.; Braun, M.; Nesener, E.; Ruhlmann, K. J.
Organomet. Chem. 1973, 49(1), 149–156.
¨
Scheme 1.
6. Couret, C.; Escudie, J.; Satge, J.; Anh, N. T.; Soussan, G.
J. Organomet. Chem. 1975, 91, 11–30.
7. Reisser, M.; Maier, A.; Maas, G. Synlett 2002, 1459–1462.
8. Hayashi, M.; Matsuura, Y.; Watanabe, Y. Tetrahedron
Lett. 2004, 45, 1409–1411.
results clearly suggested that equilibrium may exist at
the first addition step. Then, the stabilized intermediate
successively added to the electrophile resulting in
the adduct.
9. Typical procedure: Silylphosphine 2 (72mg, 0.24mmol) in
DMF (1.5mL) and THF solution of tetra-n-butylammo-
nium fluoride (1.0M, 0.2mL) were added to a stirred
mixture of styrene 1a (21mg, 0.2mmol) at rt. After stirring
for 15min at rt, the solvent was removed in vacuo. The
residue was purified by column chromatography on silica
gel (eluent: CHCl3/n-hexane = 1:4, Rf 0.4) resulting in
adduct 3a (47mg, 89%), which is a colorless oil.
The phosphination of carbon–carbon unsaturated
bonds is of interest in recent times, due to the wide
use of functional phosphines as ligands in catalysis.12,13
Base-catalyzed,14 metal-catalyzed,15 and uncatalyzed16
phosphination of alkenes and alkynes have been exten-
sively studied in recent years. The present fluoride-medi-
ated phosphination proceeded smoothly under quite
mild conditions. It produced results similar to other
methods for simple addition, in terms of yields and
selectivities. Moreover, it has the advantage that the car-
bon frame of the adduct can be extended through the
subsequent coupling reaction in one pot, thereby result-
ing in more functionalized phosphines.
10. Blinn, D. A.; Button, R. S.; Ferazi, V.; Neeb, M. K.;
Tapley, C. L.; Trehearne, T. E.; West, S. D.; Kruger, T. L.;
Storhoff, B. N. J. Organomet. Chem. 1990, 393, 143–152.
11. Typical procedure: TASF (134mg, 0.50mmol) was added
to a stirred mixture of 1d (42mg, 0.42mmol), silylphos-
phine 2 (150mg, 0.50mmol), and benzaldehyde (43mg,
0.42mmol) in DMF (3mL) at rt. After stirring for 3h at rt,
the solvent was removed in vacuo. The residue was
purified by column chromatography on silica gel (eluent:
AcOEt/n-hexane = 1:4) resulting in adduct 7 (160mg,
97%) as a mixture of diastereomers (isomer ratio = 3:2),
In conclusion, we have developed a novel phosphination
reaction of alkenes and alkynes by silylphosphines that
is mediated by TBAF. Formation of a carbon–phospho-
rus bond through a mild and convenient procedure has
paved the way for obtaining a variety of new multi-func-
tional organophosphorus compounds, particularly lig-
ands of transition metal catalysts.
1
which is difficult to separate; (major isomer) H NMR d
1.14 (t, J = 7.7Hz, 3 H), 2.81 (t, J = 5.1Hz, 2H), 3.10 (dt,
J = 7.6, 5.1Hz, 1H), 3.92 (m, 2H), 4.90 (d, J = 7.6Hz, 1H),
7.27–7.51 (m, 10H), 7.60–7.73 (m, 5H); 13C NMR d 13.6,
29.1 (d, J = 70.8Hz), 47.9 (d, J = 2.5Hz), 60.9, 75.2 (d,
J = 8.5Hz), 126.5, 127.9, 128.6 (d, J = 4.1Hz), 128.8, 130.7
(d, J = 9.6Hz), 131.2 (d, J = 9.7Hz), 132.1 (d, J = 2.4Hz),
132.7, 141.2, 172.8 (d, J = 6.7Hz); 31P NMR d À18.4; IR
(neat) 3091, 3048, 3004, 2956, 1730, 1591, 1448, 1320,
1251, 1032, 781, 704cmÀ1; FABMS calcd for C24H25O3P,
Acknowledgements
The authors thank Venture Business Laboratory of
Ehime University for their financial support. We also
thank Center for Cooperative Research and Develop-
ment, Ehime University for measurement of mass spec-
tra. This work was supported by the Fujisawa
Foundation and Saneyoshi Scholarship Foundation.
1
392; found 393 (M + H). (minor isomer) H NMR d 1.05
(t, J = 8.0Hz, 3 H), 2.35 (m, 2H), 3.80 (m, 2H), 5.14 (d,
J = 4.8Hz, 1H), 7.23–7.51 (m, 10H), 7.60–7.73 (m, 5H);
31P NMR d À19.2. These two diastereomers could be
separated by a column chromatography on silica gel
(eluent: AcOEt/n-hexane = 3:2) as their phosphine oxides
after oxidation by mCPBA.
12. Alonso, F.; Beletsukaya, I. P.; Yus, M. Chem. Rev. 2004,
104, 3148–3150.
13. Wicht, D. K.; Glueck, D. S. In Catalytic Heterofunction-
Supplementary data
alization; Togni, A., Grutzmacher, H., Eds.; Wiley-VCH
¨
Supplementary data associated with this article can be
Verlag GmbH: Weinheim, 2001; pp 143–170.
14. Bunlaksananusorn, T.; Knochel, P. Tetrahedron Lett.
2002, 43, 5817–5819.
15. (a) Shulyupin, M. O.; Kazankova, M. A.; Beletsukaya, I.
P. Org. Lett. 2002, 4, 761–763; (b) Takaki, K.; Koshoji,
G.; Komeyama, K.; Takeda, M.; Shishido, T.; Kitani, A.;
Takehira, K. J. Org. Chem. 2003, 68, 6554–6565.
16. (a) Mimeau, D.; Delacroix, O.; Gaumont, A. C. Chem.
Commun. 2003, 2928–2929; (b) Mimeau, D.; Gaumont, A.
C. J. Org. Chem. 2003, 68, 7016–7022.
References and notes
1. Omac, J. Application of Organometallic Compounds;
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