破解穴状配体：金属导向的磷酰基取代间苯二酚芳烃的切断
Cracking cavitands: metal-directed scission of phosphinyl-substituted resorcinarenes.
作者信息
Chavagnan Thierry, Sémeril David, Matt Dominique, Harrowfield Jack, Toupet Loïc
机构信息
Laboratoire de Chimie Inorganique Moléculaire et Catalyse, Institut de Chimie UMR 7177 CNRS-Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg cedex (France).
出版信息
Chemistry. 2015 Apr 27;21(18):6678-81. doi: 10.1002/chem.201500177. Epub 2015 Mar 20.
Resorcinarene-derived tetramethylene cavitands bearing a diphenylphosphino group grafted to their wider rim undergo facile, directed C-O bond breaking upon reaction with transition-metal ions in the presence of nucleophiles. One possible reaction mechanism involves formation of a P,O-chelate complex, which weakens the adjacent O-CH2 bond, leading to the formation of an oxacarbenium intermediate.
在其较宽边缘接枝有二苯基膦基团的间苯二酚芳烃衍生的四亚甲基穴状配体，在亲核试剂存在下与过渡金属离子反应时，会发生 facile、定向的 C-O 键断裂。一种可能的反应机理涉及形成 P,O-螯合配合物，该配合物会削弱相邻的 O-CH2 键，从而导致形成氧杂环庚三烯鎓中间体。
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