Synthesis of Monomers for Oxygen Enrichment Membrane

1. 在Pd (PPh_3)_4存在下，末端乙炔与Me_3SiI(1)和二烷基锌试剂反应得到乙烯基硅烷。在所有情况下，三甲基硅基加到乙炔的末端碳上，烷基被引入到内部碳上。芳香族末端乙炔和脂肪族末端乙炔都能进行高区域选择性和立体选择性的偶联反应。在RuHCl (CO) (PPh_3)_3催化下，乙烯与烯丙基三甲基硅烷(2)发生脱氢硅基化反应，产率为66%。4-氯和4-甲氧基苯乙烯以及2-乙烯基萘与2的反应可得到相应的(E) - β取代乙烯基硅烷，产率为49% ~ 76%。在PdCl_2的存在下，三甲基戊基氰化物（Me_3GeCN,3）与末端芳基乙炔反应，在具有高区域选择性的碳-碳三键上加成3，得到高产率的-氰基日耳曼。立体选择性取决于芳香环上取代基的电子性质。末端脂肪族乙炔的反应也产生了高区域选择性和立体选择性的加合物。

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.