Reactivity of Dialumane and "Dialumene" Compounds toward Alkenes

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 butadiene...

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Bibliographic Details
Published in:Chemistry : a European journal 2013-09, Vol.19 (36), p.12059-12066
Main Authors: Zhao, Yanxia, Lei, Yibo, Dong, Qingsong, Wu, Biao, Yang, Xiao-Juan
Format: Article
Language:English
Subjects:
Alkenes
aluminum
Computation
Cycloaddition
Insertion
Oxidation
Precursors
reaction mechanisms
Stilbene
Styrenes
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Summary: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. Al shook up: The reactions of [L(thf)AlAl(thf)L] (1, L=α‐diimine; see scheme) with stilbene and styrene afforded the oxidation/insertion products. In the presence of Na metal, compound 1 reacted with butadienes to yield aluminacyclopentenes as [1+4] cycloaddition products and 1,6‐dialumina‐3,8‐cyclodecadiene as a [2+4] cycloaddition product.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201300735