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Rare-Earth Silylamide-Catalyzed Selective Dimerization of Terminal Alkynes and Subsequent Hydrophosphination in One Pot

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posted on 2005-09-02, 00:00 authored by Kimihiro Komeyama, Tomonori Kawabata, Katsuomi Takehira, Ken Takaki
Rare-earth silylamides, Ln[N(SiMe3)2]3 (Ln = Y, La, Sm), catalyzed regio- and stereoselective dimerization of terminal alkynes in the presence of amine additives to give conjugated enynes in high yields. The additives played a crucial role to depress the oligomerization and to control the regio- and stereochemistry of the dimerization. Thus, the selectivity for (Z)-head-to-head enynes was increased in the order of tertiary < secondary < primary amine additives. On the other hand, the reversed order was observed for the formation of head-to-tail dimers. When α,ω-diynes were subjected to the dimerization, very novel cyclic bisenyne compounds were given through double-dimerization in satisfactory yields. In addition, an application of the system allowed subsequent hydrophosphination of the enynes generated in situ with diphenylphosphine, giving rise to 1-phosphinyl-1,3-dienes as the sole products in excellent yields after oxidative workup.

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    The Journal of Organic Chemistry

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