S. Nagata et al. / Tetrahedron Letters 48 (2007) 6637–6640
6639
Chapter 15; (b) Ogawa, A. In Handbook of Organopalla-
dium Chemistry for Organic Synthesis; Negishi, E., Ed.;
Wiley-Interscience: New York, 2002, Chapter VII.6; (c) El
Ali, B.; Alper, H. In Handbook of Organopalladium
Chemistry for Organic Synthesis; Negishi, E., Ed.; Wiley-
Interscience: New York, 2002, Chapter VI.2.1.1.2; (d)
Kuniyasu, H. In Catalytic Heterofunctionalization; Togni,
A., Grutzmacher, H., Eds.; Wiley-VCH: Weinheim, 2001,
¨
Chapter 7; (e) Ogawa, A. J. Organomet. Chem. 2000, 611,
463.
phenylacetylene (98 at.% D), which provided the vinyl-
phosphine oxide bearing two deuteriums on the termi-
nal vinylic carbon (Eq. 3). Deuterium in C6D6 was not
incorporated into the product. This result strongly sug-
gests that the hydrogen source of the hydrophosphin-
ation comes from alkynic hydrogen.21 This is also
supported by the fact that the hydrophosphination of
internal alkynes did not proceed at all.
D
8. (a) Quin, L. D. A Guide to Organophosphorus Chemistry;
Wiley-Interscience: New York, 2000; (b) Kolodiazhnyi, O.
I. Phosphorus Ylides; Wiley-VCH: Weinheim, 1999; (c)
Pd(OAc)2 5 mol% [O]
C6D6, 80 ˚C, 18 h
Ph
ð3Þ
Ph
D
(Ph2P)2
D
Ph2P
(98 atom% D)
O
Johnson, C. R.; Imamoto, T. J. Org. Chem. 1987, 52,
´
In summary, we have developed the highly regioselective
hydrophosphination of terminal alkynes with tetra-
phenyldiphosphine catalyzed by palladium diacetate,
which affords the corresponding 2-(diphenylphosph-
ino)-1-alkenes in good yields. A detailed mechanistic
study is now under investigation.
´
2170; (d) Pietrusiewicz, K. M.; Wisniewski, W.; Zablocka,
M. Tetrahedron 1989, 45, 337; (e) Minami, T.; Mot-
oyoshiya, J. Synthesis 1990, 333; (f) Xi, Z.; Zhang, W.-X.;
Song, Z.; Zheng, W.; Kong, F.; Takahashi, T. J. Org.
Chem. 2005, 70, 8785.
9. (a) Tzschach, V. A.; Baensch, S. J. Prakt. Chem. 1971,
313, 254; (b) Sato, A.; Yorimitsu, H.; Oshima, K. Angew.
Chem. Int. Ed. 2005, 44, 1694; (c) Kawaguchi, S.; Nagata,
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A. G.; Pringle, P. G.; Woodward, G. Organometallics
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10. For the transition-metal-catalyzed hydrophosphinylation
to unsaturated bonds, see: (a) Han, L.-B.; Tanaka, M. J.
Am. Chem. Soc. 1996, 118, 1571; (b) Han, L.-B.; Choi, N.;
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Acknowledgments
This work is supported by Grant-in-Aid for Scientific
Research on Priority Areas (Area 444, No. 18037064)
and Scientific Research (B, 19350095), from the Minis-
try of Education, Culture, Sports, Science and Technol-
ogy, Japan. We gratefully acknowledge Professor L.-B.
Han (National Institute of Advanced Industrial Science
and Technology (AIST)) for his helpful suggestions.
`
Tanaka, M. J. Org. Chem. 2001, 66, 5929; (f) Deprele, S.;
Montchamp, J.-L. J. Am. Chem. Soc. 2002, 124, 9386; (g)
Allen, A., Jr.; Ma, L.; Lin, W. Tetrahedron Lett. 2002, 43,
3707; (h) Milton, M. D.; Onodera, G.; Nishibayashi, Y.;
Uemura, S. Org. Lett. 2004, 6, 3993; (i) Han, L.-B.; Zhang,
C.; Yazawa, H.; Shimada, S. J. Am. Chem. Soc. 2004, 126,
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