4672
N. Dobashi et al. / Tetrahedron Letters 48 (2007) 4669–4673
S. M.; Ding, M. J. Chem. Soc., Perkin Trans. 1 2000, 1771;
allics 1996, 15, 3259; (c) Han, L.-B.; Hua, R.; Tanaka, M.
Angew. Chem., Int. Ed. 1998, 37, 94; (d) Zhao, C.-Q.; Han,
L.-B.; Goto, M.; Tanaka, M. Angew. Chem., Int. Ed 2001,
40, 1929; (e) Han, L.-B.; Zhao, C.-Q.; Tanaka, M. Int.
Patent WO2002/064604; (f) Han, L.-B.; Zhang, C.;
Tanaka, M. Int. Patent WO2003/097654.
(c) Mizushima, E.; Han, L.-B.; Hayashi, T. Tanaka, M.
Jpn. Patent 3,610,371, 2004; (d) Demchuk, O. M.;
Pietrusiewicz, K. M.; Michrowska, A.; Grela, K. Org.
Lett. 2003, 5, 3217; (e) Kobayashi, Y.; William, A. D. Adv.
Synth. Catal. 2004, 346, 1749; (f) Leca, D.; Song, K.;
Albert, M.; Gonc¸alves, M. G.; Fensterbank, L.; Lacoˆte,
E.; Malacria, M. Synthesis 2005, 1405; (g) Michrowska,
A.; Bujok, R.; Harutyunyan, S.; Sashuk, V.; Dolgonos,
G.; Grela, K. J. Am. Chem. Soc. 2004, 126, 9318; (h)
Rahman, M. S.; Oliana, M.; Hii, K. K. Tetrahedron:
Asymmetry 2004, 15, 1835; (i) Alajarin, M.; Lopez-
Leonardo, C.; Llamas-Lorente, P. Lett. Org. Chem.
2004, 1, 145; (j) Saratovskikh, I. V.; Ragulin, V. V. Russ.
J. Gen. Chem. 2005, 75, 1077; (k) Ono, Y.; Han, L.-B.
Tetrahedron Lett. 2006, 47, 421.
8. Quite recently Oshima and co-workers reported an elegant
radical reaction involving chlorodiphenylphosphine,
diphenylphosphine, triethylamine, and a terminal alkyne
leading to a 1,2-bis(diphenylphosphino)alkene, which
could be readily oxidized with hydrogen peroxide to
furnish a 1,2-bis(diphenylphosphinyl)alkene. See: Sato, A.;
Yorimitsu, H.; Oshima, K. Angew. Chem., Int. Ed. 2005,
44, 1694.
9. It has been known that palladium acetate is reduced to
generate Pd(0) species when treated with a phosphine; see:
(a) Amatore, C.; Jutand, A.; M’Barki, M. A. Organomet-
2. (a) Welch, F. J.; Paxton, H. J. J. Polym. Sci., Part A: Gen.
Pap. 1965, 3, 3427; (b) Welch, F. J.; Paxton, H. J. J.
Polym. Sci., Part A: Gen. Pap. 1965, 3, 3439; (c) Shukla, J.
R. U.S. Patent 4,241,145, 1980; (d) Levchik, S. V.; Weil, E.
D. Polym. Int. 2005, 54, 11.
3. (a) Brunner, H.; Pro¨bster, M. Inorg. Chim. Acta 1982, 61,
129; (b) Brown, J. M.; Lucy, A. R. J. Organomet. Chem.
1986, 314, 241; (c) Krause, H.; Do¨bler, C. Catal. Lett.
1991, 8, 23; (d) Okada, Y.; Minami, T.; Yamamoto, T.;
Ichikawa, J. Chem. Lett. 1992, 547; (e) Yamazaki, A.;
Achiwa, I.; Horikawa, K.; Tsurubo, M.; Achiwa, K.
Synlett 1997, 455.
´
allics 1992, 11, 3009; (b) Amatore, C.; Carre, E.; Jutand,
A.; M’Barki, M. A. Organometallics 1995, 14, 1818.
10. (a) Double addition has been documented. See: (a) Ref.
6h; (b) Allen, A., Jr.; Manke, D. R.; Lin, W. Tetrahedron
Lett. 2000, 41, 151.
11. In view of possible oligomerization of 1a, we used a slight
excess of 1a. For clearer understanding of the reaction
profile forming both single and double phosphinylated
products (3a, 4a, 5a, and 6a), however, the product yields
in this particular reaction were tentatively calculated based
on the quantity of 1a charged.
4. (a) Rojas, R.; Valderrama, M.; Garland, M. T. J.
Organomet. Chem. 2004, 689, 293; (b) Ueno, S.; Shino-
hara, T.; Aramata, M.; Tanifuji, Y.; Inukai, T.; Ishizaka
H. U.S. Patent 6,894,181, 2005.
5. For selected examples, see: (a) Chmutova, M. K.;
Kochetkova, N. E.; Myasoedov, B. F. J. Inorg. Nucl.
Chem. 1980, 42, 897; (b) Rosen, M.; Nikolotova, Z. I.;
Kartasheva, N. A. Radiokhim. 1990, 32, 70; (c) Kabach-
nik, M. I. Heteroatom Chem. 1991, 2, 1.
6. For recent reviews, see: (a) Dembitsky, V. M.; Quntar, A.
A. A. A.; Haj-Yehia, A.; Srebnik, M. Mini-Rev. Org.
Chem. 2005, 2, 91; (b) Tanaka, M. Top. Curr. Chem. 2004,
232, 25; For selected recent examples, see: (c) Niu, M.; Fu,
H.; Jiang, Y.; Zhao, Y. Chem. Commun. 2007, 272; (d)
Thielges, S.; Bisseret, P.; Eustache, J. Org. Lett. 2005, 7,
681; (e) Han, L.-B.; Zhao, C.-Q. J. Org. Chem. 2005, 70,
10121; (f) Montchamp, J.-L. J. Organomet. Chem. 2005,
690, 2388; (g) Ribiere, P.; Bravo-Altamirano, K.; Antczak,
M. I.; Hawkins, J. D.; Montchamp, J.-L. J. Org. Chem.
2005, 70, 4064; (h) Stone, J. J.; Stockland, R. A., Jr.;
Reyes, J. M., Jr.; Kovach, J.; Goodman, C. C.; Tillman, E.
S. J. Mol. Catal. A: Chem. 2005, 226, 11; (i) Maffei, M.
Curr. Org. Synth. 2004, 1, 355; (j) Tayama, O.; Nakano,
A.; Iwahama, T.; Sakaguchi, S.; Ishii, Y. J. Org. Chem.
12. The higher branch-selectivity in this experiment (100 ꢁC),
as compared with the branch-selectivity (<5%) observed at
70 ꢁC suggests that the higher reaction temperature is also
a factor that enhances the branch-selectivity. See Ref. 7b.
13. Conversions of diphenylphosphine oxide in the reactions
run in n-octane and ethanol were only 40% and 18%,
respectively.
14. Typical procedure: A mixture of Pd(OAc)2 (0.067 mmol),
dppe (0.10 mmol), diphenylphosphine oxide (1.33 mmol),
and p-tolylacetylene (1.39 mmol) dissolved in propionitrile
(5 mL) was heated at 100 ꢁC for 3 h. The resulting mixture
was evaporated and analyzed by 1H NMR spectroscopy in
CDCl3 using p-dimethoxybenzene as internal standard.
Evaporation of CDCl3 and column chromatography using
hexane/ethyl acetate (1/1) afforded 3a in 83% yield.
15. Despite the low yield of 4k, 5k, and 6k were not formed at
all. We thank reviewers who recommended us to examine
the reaction of trimethylsilylacetylene, which displayed the
exceptional behavior.
16. Secondary phosphine oxides exist in two tautomeric
isomers, P(O)H and P(OH), the former being dominant
in the equilibrium. See: (a) Bailey, W. J.; Fox, R. B. J. Org.
Chem. 1963, 28, 531; (b) Bailey, W. J.; Fox, R. B. J. Org.
Chem. 1964, 29, 1013; (c) Hamilton, L. A.; Landis, P. S..
In Organic Phosphorus Compounds; Kosolapoff, G. M.,
Maier, L., Eds.; Wiley: New York, 1972; Vol. 4, Chapter
11.
17. Obtained from a mixture resulting from an uncatalyzed
reaction of (p-tolylethynyl)diphenylphosphine oxide (8)
with 2 run at 100 ꢁC for 3 h in toluene (vide infra).
18. In the present reaction of p-tolylacetylene, we do have
`
2004, 69, 5494; (k) Deprele, S.; Montchamp, J.-L. Org.
Lett. 2004, 6, 3805; (l) Kabalka, G. W.; Guchhait, S. K.
Org. Lett. 2003, 5, 729; (m) Gelman, D.; Jiang, L.;
Buchwald, S. L. Org. Lett. 2003, 5, 2315; (n) Gulykina, N.
S.; Dolgina, T. M.; Bondarenko, G. N.; Beletskaya, I. P.
Russ. J. Org. Chem. 2003, 39, 797; (o) Takaki, K.;
Koshoji, G.; Komeyama, K.; Takeda, M.; Shishido, T.;
Kitani, A.; Takehira, K. J. Org. Chem. 2003, 68, 6554; (p)
Quntar, A. A. A. A.; Dembitsky, V. M.; Srebnik, M. Org.
Lett. 2003, 5, 357; (q) Peng, A.; Ding, Y. Synthesis 2003,
205; (r) Takaki, K.; Komeyama, K.; Takehira, K. Tetra-
hedron 2003, 59, 10381; (s) Bisaro, F.; Gouverneur, V.
Tetrahedron Lett. 2003, 44, 7133; (t) Lera, M.; Hayes, C. J.
Org. Lett. 2001, 3, 2765; (u) Beghetto, V.; Matteoli, U.;
Scrivanti, A. Chem. Commun. 2000, 155.
detected
oxide.
a trace of (p-tolylethynyl)diphenylphosphine
19. Prepared by hydrogen peroxide oxidation of (p-tolylethyn-
yl)diphenylphosphine. See: Liu, B.; Wang, K. K.; Peter-
sen, J. L. J. Org. Chem. 1996, 61, 8503; Beletskaya, I. P.;
Afanasiev, V. V.; Kazankova, M. A.; Efimova, I. V. Org.
Lett. 2003, 5, 4309.
20. Han, L.-B.; Tanaka, M. Shokubai 1999, 41, 577.
21. For selected examples of apparent trans-insertion involv-
ing late transition metal complexes, see: (a) Green, M.;
7. (a) Han, L.-B.; Tanaka, M. J. Am. Chem. Soc. 1996, 118,
1571; (b) Han, L.-B.; Choi, N.; Tanaka, M. Organomet-