Unexpected C=C bond formation via doubly dehydrogenative coupling of two saturated sp3 C-H bonds activated with a polymolybdate
Unexpected C=C bond formation via doubly dehydrogenative coupling of two saturated sp3 C-H bonds activated with a polymolybdate
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DOI：
10.1021/ja070600z
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发表时间：
2007-05-09
影响因子：
15
通讯作者：
Wang, Longsheng
中科院分区：
文献类型：
--
作者：
Li, Qiang;Wei, Yongge;Wang, Longsheng
在这次通信中，我们证明了多钼酸盐可以激活脂肪胺中的sp(3)C-H键。出人意料的是，通过两个脂肪族伯胺在含六钼酸根的氮原子附近的两个sp(3)C-H键的活化和脱氢耦合，形成了碳-碳双键。详细的实验包括H-1核磁共振、C-13核磁共振、IR、UV-Vis、ESI-MS，特别是X-射线单晶衍射，基本上证实了一类有机-无机杂化分子中碳-碳双键的存在，这些杂化分子由两个末端取代的亚胺六钼酸盐笼通过反式四取代、共轭、刚性的乙烯体系桥联而成。这一发现可能开辟了一条有趣的道路，直接通过饱和C-H键的官能化来阐述CC双键。
In this communication, we demonstrate that polyoxomolybdates can activate sp(3) C-H bonds in aliphatic amines. Unexpectedly, a carbon-carbon double bond is formed from two aliphatic primary amines via the activation and dehydrogenative coupling of two sp(3) C-H bonds near the nitrogen atom bearing a hexamolybdate. Detailed experiments including H-1 NMR, C-13 NMR, IR, UV-vis, ESI-MS, and especially X-ray single-crystal diffraction substantially confirm the existence of carbon-carbon double bonds in a class of so-resulting organic-inorganic hybrid molecules, which are made up of two terminally substituted imidohexamolybdate cages bridged by a trans-tetrasubstituted, conjugated, rigid ethylene system. This discovery perhaps opens an interesting road to elaborate the CC double bond directly via the functionalization of saturated C-H bonds.