Pécharman Anne-Frédérique, Hill Michael S, Mahon Mary F
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.
Angew Chem Int Ed Engl. 2018 Aug 13;57(33):10688-10691. doi: 10.1002/anie.201803607. Epub 2018 Jun 28.
Reactions of readily accessible magnesium-centered pinacolatoboryl nucleophiles with [(Ph B) O] result in B-O bond activation of the diphenylborinic anhydride. Although [pinBBPh ] is apparently generated when the nucleophilic boron unit is derived in situ from a magnesium diboranate, it cannot be isolated owing to its onward derivatization by a further {Bpin} equivalent. A reaction with a terminal magnesium boryl species similarly provides a boryloxide byproduct. In this case, however, the unsymmetrical B(sp )-B(sp ) diborane may be intercepted as its DMAP adduct.
易于获得的以镁为中心的频哪醇硼酸酯亲核试剂与[(PhB)O]反应，导致二苯基硼酸酐的B-O键活化。尽管当亲核硼单元原位衍生自二硼酸镁时显然会生成[pinBBPh]，但由于其会被另一个{Bpin}当量进一步衍生化，所以无法分离得到。与末端镁硼基物种的反应同样会产生一种硼氧化物副产物。然而，在这种情况下，不对称的B(sp)-B(sp)二硼烷可以作为其DMAP加合物被截获。
