Palladium-catalyzed cross-addition of triisopropylsilylacetylene to unactivated alkynes

Pure and Applied Chemistry, May, 2008 by Naofumi Tsukada, Satoshi Ninomiya, Yoshimi Aoyama, Yoshio Inoue

ACKNOWLEDGMENT

This work was supported by a Grant-in-Aid for Scientific Research (No. 17750081) from MEXT.

REFERENCES

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[2.] R. Ghosh, X. Zhang, P. Achord, T. J. Emge, K. Krogh-Jespersen, A. S. Goldman. J. Am. Chem. Soc. 129, 853 (2007) and refs. cited therein.

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[6.] (a) B. M. Trost, C. Chan, G. Ruhter. J. Am. Chem. Soc. 109, 3486 (1987); (b) B. M. Trost, C.-J. Li. Synthesis 1267 (1994); (c) B. M. Trost, A. E. Harms. Tetrahedron Lett. 37, 3971 (1996); (d) B. M. Trost, M. T. Sorum, C. Chan, A. E. Harms, G. Ruhter. J. Am. Chem. Soc. 119, 698 (1997); (e) B. M. Trost, M. C. McIntosh. Tetrahedron Lett. 38, 3207 (1997). See also: (f) L. Chen, C.-J. Li. Tetrahedron Lett. 45, 2771 (2004); (g) T. Hirabayashi, S. Sakaguchi, Y. Ishii. Adv. Synth. Catal. 347, 872 (2005).

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[10.] Preliminary results of this work have been previously reported: N. Tsukada, S. Ninomiya, Y. Aoyama, Y. Inoue. Org. Lett. 9, 2919 (2007).

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[12.] (a) N. Tsukada, T. Mitsuboshi, H. Setoguchi, Y. Inoue. J. Am. Chem. Soc. 125, 12102 (2003); (b) N. Tsukada, K. Murata, Y. Inoue. Tetrahedron Lett. 46, 7515 (2005); (c) N. Tsukada, H. Setoguchi, T. Mitsuboshi, Y. Inoue. Chem. Lett. 35, 1164 (2006).

* Paper based on a presentation at the 14th International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-14), 2-6 August 2007, Nara, Japan. Other presentations are published in this issue, pp. 807-1194.

Naofumi Tsukada ([double dagger]), Satoshi Ninomiya, Yoshimi Aoyama, and Yoshio Inoue

Graduate School of Engineering, Tohoku University, Aoba, Sendai 980-8579, Japan

([double dagger]) Corresponding author

Table 1 Reaction of TIPSA with 3-hexyne in the presence of
various palladium catalysts. (a)

Entry    Catalyst                             Yield of     TIPSA
                                               3 (%)      dimers
                                                             (%)

    1    5                                      94           4
    2    [Pd.sub.2][(dba).sub.3]  1             73           2
    3    Pd[(P[Ph.sub.3]).sub.4]                 2          35
    4    Pd[(OAc).sub.2]   TDMPP                17          72
    5    Pd[(OAc).sub.2]   dppe                 36          39
    6    [Pd.sub.2][(dba).sub.3]   dppf          5           8
    7    [Pd.sub.2][(dba).sub.3]   6             2           4
    8    [Pd.sub.2][(dba).sub.3]   7             7           5
    9    [Pd.sub.2][(dba).sub.3]   8a            3           5
   10    [Pd.sub.2][(dba).sub.3]   8b           41          14
   11    [Pd.sub.2][(dba).sub.3]   8c           60          18
   12    [Pd.sub.2][(dba).sub.3]   8d           45          24
   13    [Pd.sub.2][(dba).sub.3]   8e           50          25
   14    [Pd.sub.2][(dba).sub.3]   9             1           0

(a) A mixture of TIPSA (0.5 mmol), 3-hexyne (0.5 mmol), and a catalyst
(2 mol %) in toluene (2.0 mL) was heated at 110 [degrees]C.