Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides

Rami J. Batrice; Christos E. Kefalidis; Laurent Maron; Moris S. Eisen

doi:10.1021/jacs.5b12731

Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides

Rami J. Batrice, Christos E. Kefalidis, Laurent Maron, Moris S. Eisen^*

^*Corresponding author for this work

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

44 Scopus citations

Abstract

The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U[N(SiMe₃)₂]₃ and [(Me₃Si)₂N]₂An[κ²-(N,C)-CH₂Si(CH₃)₂N(SiMe₃)] (An = Th or U), alcohol additions to unsaturated carbon-nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide-oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle.

Original language	English
Pages (from-to)	2114-2117
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	7
DOIs	https://doi.org/10.1021/jacs.5b12731
State	Published - 2 Mar 2016
Externally published	Yes

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title = "Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides",

abstract = "The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ2-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U), alcohol additions to unsaturated carbon-nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide-oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle.",

author = "Batrice, {Rami J.} and Kefalidis, {Christos E.} and Laurent Maron and Eisen, {Moris S.}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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doi = "10.1021/jacs.5b12731",

language = "英语",

volume = "138",

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T1 - Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides

AU - Batrice, Rami J.

AU - Kefalidis, Christos E.

AU - Maron, Laurent

AU - Eisen, Moris S.

PY - 2016/3/2

Y1 - 2016/3/2

N2 - The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ2-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U), alcohol additions to unsaturated carbon-nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide-oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle.

AB - The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ2-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U), alcohol additions to unsaturated carbon-nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide-oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 7

ER -

Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides

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