Tris(pentafluorophenyl)borane-Catalyzed Reaction of Phosphorus/Boron and Nitrogen/Boron Frustrated Lewis Pair Dihydrogen Activation Products with Alkenes and Alkynes
Tris(pentafluorophenyl)borane-Catalyzed Reaction of Phosphorus/Boron and Nitrogen/Boron Frustrated Lewis Pair Dihydrogen Activation Products with Alkenes and Alkynes
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DOI：
10.1002/cctc.201601229
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发表时间：
2017-02-01
期刊：
影响因子：
4.5
通讯作者：
Erker, Gerhard
中科院分区：
文献类型：
--
作者：
Wang, Tongdao;Jentgens, Xenia;Erker, Gerhard
N/B受阻Lewis对(FLP)二氢裂解产物10在B(C6F5)(3)催化下与苯乙炔发生区域选择性的反-1，2-氢化硼加成反应，得到含顺式苯乙烯基的铵/硼两性离子12。B(C6F5)(3)催化的10与1-苯丙炔的反应类似地得到了13。我们得到的证据表明，该反应是由所涉及的两个B中心之间的氢化物迁移引发的，然后分别通过氢化物与硼烷活化的炔烃或烯烃的加成来继续进行。在B(C6F5)(3)催化下，由乙烯桥联的P/B FLP 3得到的氢-2裂解产物4与这些炔烃和苯乙烯发生类似的反应，生成相应的烯基或烷基硼酸酯产物。用X射线衍射仪对新加成产物进行了表征。
The N/B frustrated Lewis pair (FLP) dihydrogen splitting product 10 undergoes a facile B(C6F5)(3)-catalyzed regioselective trans-1,2-hydridoborate addition reaction to phenylacetylene to give the cis-styryl-containing ammonium/borate zwitterion 12. The B(C6F5)(3)-catalyzed reaction of 10 with 1-phenylpropyne proceeded analogously to give 13. The respective [B]/H- addition to styrene gave the corresponding [B]-CH2CH2Ph-containing product 14 under mild conditions. We obtained evidence that the reaction is initiated by hydride migration between the two B centers involved and is then continued by hydride addition to the borane activated alkyne or alkene, respectively. The H-2-splitting product 4 derived from the ethylene-bridged P/B FLP 3 reacted analogously with these alkynes and also with styrene under B(C6F5)(3) catalysis to yield the respective alkenyl- or alkyl borate products. The new addition products were characterized by using XRD.