The tandem reduction/oxidation of fluorenyl compounds was performed with LiAlH4 under air to afford the corresponding 9-hydroxyfluorenyl derivatives in good yields. This methodology with LiAlH4 is unprecedented and most likely proceeds by an organoaluminium intermediate, and in the proposed mechanism.
New Approach to Substrate Activation or How Heterobimetallic Complexes {[(<i>p</i>-<i>t</i>Bu-C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>CH]<sub>3</sub>M}K (M = Ca and Yb) Make Intermolecular Olefin Hydroamination and NH<sub>3</sub> Cascade Hydroamination/Hydroaminomethylation Feasible
作者:Alexander N. Selikhov、Anton V. Cherkasov、Yulia V. Nelyubina、Alexander A. Trifonov
DOI:10.1021/acscatal.3c03471
日期:2023.10.6
unprecedented catalyticactivity and 100% regioselectivity in intermolecular olefin hydroamination allowing to involve into the reaction a broad scope of substrates including ethylene (1 atm), internal C═C bonds, and a variety of primary and secondary amines. Complex 1Ca allowed for the cascade NH3 alkylation with styrene and hydroaminoalkylation involving one of styryl fragments to afford N,N-diphenethyl-1
在这里,我们报道了两种热稳定的无碱异双金属二苯甲基配合物[( p - t BuC 6 H 4 ) 2 CH] 3 M}K (M = Yb(II) 和 Ca(II)) 的合成和结构,其特征在于接触离子对的结构,其中阴离子部分由三个二苯甲基配体 η 3组成,与三个 η 6封装的 M(II) 离子和 K +阳离子配位-配位苯环。该配合物在分子间烯烃加氢胺化中表现出前所未有的催化活性和 100% 区域选择性,允许广泛的底物参与反应,包括乙烯 (1 atm)、内部 C=C 键以及各种伯胺和仲胺。络合物1Ca允许与苯乙烯进行级联NH 3烷基化和涉及苯乙烯基片段之一的氢氨基烷基化,得到N , N-二苯乙基-1,4-二苯基丁-2-胺。