Reactivity of dialumane and "dialumene" compounds toward alkenes

Yanxia Zhao; Yibo Lei; Qingsong Dong; Biao Wu; Xiao Juan Yang

doi:10.1002/chem.201300735

Reactivity of dialumane and "dialumene" compounds toward alkenes

Yanxia Zhao, Yibo Lei, Qingsong Dong, Biao Wu, Xiao Juan Yang^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

37 Citations (Scopus)

Abstract

The reactions of dialumane [L(thf)Al-Al(thf)L] (1, L=[{(2,6-iPr ₂C₆H₃)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(CH ₂C(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.

Original language	English
Pages (from-to)	12059-12066
Number of pages	8
Journal	Chemistry - A European Journal
Volume	19
Issue number	36
DOIs	https://doi.org/10.1002/chem.201300735
Publication status	Published - 2 Sept 2013
Externally published	Yes

Keywords

alkenes
aluminum
cycloaddition
insertion
reaction mechanisms

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Zhao, Y., Lei, Y., Dong, Q., Wu, B., & Yang, X. J. (2013). Reactivity of dialumane and "dialumene" compounds toward alkenes. Chemistry - A European Journal, 19(36), 12059-12066. https://doi.org/10.1002/chem.201300735

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abstract = "The reactions of dialumane [L(thf)Al-Al(thf)L] (1, L=[{(2,6-iPr 2C6H3)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(CH 2C(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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author = "Yanxia Zhao and Yibo Lei and Qingsong Dong and Biao Wu and Yang, {Xiao Juan}",

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T1 - Reactivity of dialumane and "dialumene" compounds toward alkenes

AU - Zhao, Yanxia

AU - Lei, Yibo

AU - Dong, Qingsong

AU - Wu, Biao

AU - Yang, Xiao Juan

PY - 2013/9/2

Y1 - 2013/9/2

N2 - The reactions of dialumane [L(thf)Al-Al(thf)L] (1, L=[{(2,6-iPr 2C6H3)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(CH 2C(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.

AB - The reactions of dialumane [L(thf)Al-Al(thf)L] (1, L=[{(2,6-iPr 2C6H3)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(CH 2C(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.

KW - alkenes

KW - aluminum

KW - cycloaddition

KW - insertion

KW - reaction mechanisms

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VL - 19

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EP - 12066

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

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ER -

Reactivity of dialumane and "dialumene" compounds toward alkenes

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Keywords

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