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Catalytic [2+2+1] Cross-Cyclotrimerization of Silylacetylenes and Two Alkynyl Esters To Produce Substituted Silylfulvenes


  • This work was supported partly by Grants-in-Aid for Scientific Research (Nos. 23105512, 20675002, and 21906) from MEXT (Japan). We thank Umicore for generous support in supplying rhodium complexes.


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Three become one: The cationic rhodium(I) complex [Rh(cod)2]BF4 catalyzes the [2+2+1] cross-cyclotrimerization of silylacetylenes and two alkynyl esters, leading to substituted silylfulvenes (see scheme; cod=1,5-cyclooctadiene). The reductive complexation of the silylfulvene product with RhCl3 in EtOH furnished the corresponding dinuclear electron-deficient cyclopentadienyl rhodium(III) complex.