Reactivity of Dialumane and “Dialumene” Compounds toward Alkenes |
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| Authors: | Yanxia Zhao Dr Yibo Lei Qingsong Dong Prof Biao Wu Prof Xiao‐Juan Yang |
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| Institution: | 1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, CAS, Lanzhou 730000 (P.R. China);2. Graduate University of Chinese Academy of Sciences, Beijing 100049 (P.R. China);3. College of Chemistry and Materials Science, Northwest University, Xi'an 710069 (P.R. China) |
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| Abstract: | The reactions of dialumane L(thf)Al? Al(thf)L] ( 1 , L={(2,6‐iPr2C6H3)NC(Me)}2]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. |
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| Keywords: | alkenes aluminum cycloaddition insertion reaction mechanisms |
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