Zhao Yanxia, Lei Yibo, Dong Qingsong, Wu Biao, Yang Xiao-Juan
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, CAS, Lanzhou 730000 (P.R. China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (P.R. China).
Chemistry. 2013 Sep 2;19(36):12059-66. doi: 10.1002/chem.201300735. Epub 2013 Jul 18.
The reactions of dialumane [L(thf)Al-Al(thf)L] (1, L={(2,6-iPr2C6H3)NC(Me)}2) with stilbene and styrene afforded the oxidation/insertion products [L(thf)Al(CH(Ph)-CH(Ph))AlL] (2) and [L(thf)Al(CH(Ph)-CH2)Al(thf)L] (3), respectively. In the presence of Na metal, precursor 1 reacted with butadienes, possibly through the reduced "dialumene" or the "carbene-like" :AlL species, to yield aluminacyclopentenes [LAl(CH2C(Me)=C(Me)CH2)Na]n (4 a) and [Na(dme)3][LAl(CH2C(Me)=CHCH2)] (4 b, dme=dimethoxyethane) as [1+4] cycloaddition products, as well as the [2+4] cycloaddition product 1,6-dialumina-3,8-cyclodecadiene, [{Na(dme)}2][LAl(CH2C(Me)=C(Me)CH2)2AlL] (5). The possible mechanisms of the cycloaddition reactions were studied by using DFT computations.
二铝烷[L(thf)Al - Al(thf)L] (1, L = {(2,6 - iPr₂C₆H₃)NC(Me)}₂) 与反式二苯乙烯和顺式苯乙烯反应，分别得到氧化/插入产物[L(thf)Al(CH(Ph)-CH(Ph))AlL] (2) 和 [L(thf)Al(CH(Ph)-CH₂)Al(thf)L] (3)。在金属钠存在下，前体1与丁二烯反应，可能是通过还原的“二铝烯”或“类卡宾”的:AlL物种，生成铝环戊烯[LAl(CH₂C(Me)=C(Me)CH₂)Na]ₙ (4 a) 和 [Na(dme)₃][LAl(CH₂C(Me)=CHCH₂)] (4 b, dme = 二甲氧基乙烷) 作为[1 + 4]环加成产物，以及[2 + 4]环加成产物1,6 - 二铝杂 - 3,8 - 环癸二烯，[{Na(dme)}₂][LAl(CH₂C(Me)=C(Me)CH₂)₂AlL] (5)。通过密度泛函理论计算研究了环加成反应的可能机理。
