Wang Zhizhong, Wnuk Stanislaw F
Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199, USA.
J Org Chem. 2005 Apr 15;70(8):3281-4. doi: 10.1021/jo047773g.
The oxidative treatment of vinyltris(trimethylsilyl)germanes with hydrogen peroxide (NaOH/H(2)O/THF) or tert-butyl peroxide (KH/THF) generates reactive germanol or germanoxane species that undergo Pd-catalyzed cross-couplings with aryl and alkenyl halides and aryl triflates in the presence of Pd(PPh(3))(4). Vinylgermanes having either a conjugated or isolated double bond serve as versatile transmetalation reagents. The E-germanes undergo coupling with retention of stereochemistry under aqueous and anhydrous conditions, while coupling of Z-germanes occurs with less stereoselectivity to produce a mixture of E/Z products.
用过氧化氢（NaOH/H₂O/THF）或叔丁基过氧化物（KH/THF）对乙烯基三（三甲基硅基）锗烷进行氧化处理，会生成活性锗醇或锗氧烷物种，这些物种在Pd(PPh₃)₄存在下与芳基卤化物、烯基卤化物和芳基三氟甲磺酸酯发生钯催化的交叉偶联反应。具有共轭或孤立双键的乙烯基锗烷可作为通用的转金属化试剂。E型锗烷在水性和无水条件下进行偶联时立体化学得以保留，而Z型锗烷的偶联反应立体选择性较低，会生成E/Z产物的混合物。
