Yanagisawa Tatsuya, Mizuhata Yoshiyuki, Tokitoh Norihiro
Institute for Chemical Research, Kyoto University Gokasho, Uji, Kyoto, 611-0011, Japan.
Integrated Research Consortium on Chemical Sciences Uji, Kyoto, Japan.
Chempluschem. 2020 May;85(5):933-942. doi: 10.1002/cplu.202000239.
Internal and terminal alkynes react with phosphanylalumanes, i. e., P-Al single-bond species, through heating but without any additional additives. The reactions with internal alkynes afforded the corresponding adducts with cis-1,2-form in moderate yields (54-80 %). In addition, alkyne adducts thus obtained function as P/Al-based C -vicinal FLPs, and the FLP addition reactions with benzaldehyde and CO were demonstrated. Furthermore, in the reaction of 2,4,6-trimethylphenyl-substituted alkyne adducts with dimethyl acetylenedicarboxylate, an unexpected C -C bond cleavage characteristic of this system was demonstrated.
内炔和端炔通过加热与膦亚铝烷（即P-Al单键物种）发生反应，无需任何额外添加剂。与内炔的反应以中等产率（54-80%）得到具有顺式-1,2-构型的相应加合物。此外，由此获得的炔烃加合物可作为基于P/Al的C-邻位FLP（ frustrated Lewis pairs，受阻路易斯酸碱对），并证明了其与苯甲醛和CO的FLP加成反应。此外，在2,4,6-三甲基苯基取代的炔烃加合物与二甲基乙炔二羧酸酯的反应中，证明了该体系具有意外的C-C键断裂特性。
