Synthesis of Monomers for Oxygen Enrichment Membrane

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1. The reaction of terminal acetylenes with Me_3SiI (1) and dialkylzinc reagents in the presence of Pd (PPh_3)_4 gave vinylsilanes. In all cases the trimethylsilyl group adds to the terminal carbon of the acetylenes and the alkyl group is introduced at the internal carbon. Both aromatic and aliphatic terminal acetylenes undergo the coupling reaction with high regio-and stereoselectivities.2. The reaction of stirene with allyltrimethylsilane (2) in the presence of RuHCl (CO) (PPh_3)_3 as a catalyst resulted in dehydrogenative silylation to afford (E) -1-phenyl-2- (trimethylsilyl) ethylene in 66% yield. The reactions of 4-chloro- and 4-methoxy-stirenes, and 2-vinylnaphthalene with 2 provide the corresponding (E) -beta-substituted vinylsilanes in 49-76% yields.3. The reaction of trimethylgermyl cyanide (Me_3GeCN,3) with terminal aromatic acetylenes in the presence of PdCl_2 results in the addition of 3 to the carbon-carbon triple bonds with high regioselectivity leading to beta-cyano vinylgermanes in high yields. The stereoselectivity depends on the electronic nature of the substituents on the aromatic ring. The reaction of terminal aliphatic acetylenes also afford the adduct with high regio- and stereoselectivity.