Isonitrile-Palladium(0) Complex as an Effective Catalyst for Activation of Silicon-Silicon -Bonds

We have developed a new catalyst system, an isonitrile-palladium(0) complex, for bis-silylation reactions. The complex was originally isolated and investigated by Otsuka's group (for example, S. Otsuka, A. Nakamura, Y. Tatsuno, J. Am. Chem. Soc. 1969, 91, 6994). During the course of our investigation on palladium-catalyzed insertion of isonitriles into silicon-silicon linkages of polysilanes [a,b], we found that a combinational use of t-alkyl isocyanides and Pd(OAc)2 was highly effective for the addition of hexamethyldisilane to alkynes.[c,d] The catalyst was also effective for bis-silylation of alkenes [5,6] and ring enlargement oligomerization of cyclic disilanes.[e,f]

The isonitrile-palladium(0) features a high ability to undergo oxidative addition of silicon-silicon bonds. Thus, we have successfully synthesized various cyclic bis(organosilyl)palladium(II) complexes by the oxidative addition reactions.[g,h]

References for this page

[a] Y. Ito, T. Matsuura, M. Murakami, J. Am. Chem. Soc. 1988, 110, 3692.

[b] Y. Ito, M. Suginome, T. Matsuura, M. Murakami, J. Am. Chem. Soc. 1991, 113, 3987.

[c] Y. Ito, M. Suginome, M. Murakami, J. Org. Chem. 1991, 56, 1948.

[d] M. Murakami, H. Oike, M. Sugawara, M. Suginome, Y. Ito, Tetrahedron 1993, 49, 3933.

[e] M. Suginome, H. Oike, Y. Ito, J. Am. Chem. Soc. 1995, 117, 1665.

[f] M. Suginome, H. Oike, P. H. Shuff, Y. Ito, Organometallics 1996, 15, 2170.

[g] M. Suginome, H. Oike, S.-S. Park, Y. Ito, Bull. Chem. Soc. Jpn. 1996, 69, 289.

[h] M. Suginome, H. Oike, P. H. Shuff, Y. Ito, J. Organomet. Chem. 1996, 521, 405.

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