Coupling of terminal alkynes and isonitriles by organoactinide complexes: Scope and mechanistic insights

E. Barnea; T. Andrea; J. C. Berthet; M. Ephritikhine; M. S. Eisen

doi:10.1021/om701223x

Coupling of terminal alkynes and isonitriles by organoactinide complexes: Scope and mechanistic insights

E. Barnea, T. Andrea, J. C. Berthet, M. Ephritikhine, M. S. Eisen

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Abstract

The coupling reaction of terminal alkynes with several isonitriles, catalyzed by the neutral organoactinide complexes Cp₂*AnMe ₂ (Cp* = C₅Me₅, An = Th, U) or the cationic complex [(Et₂N)₃U][BPh₄], yielded substituted α,β-acetylenic aldimines, in good to excellent yields. The reaction proceeded via a 1,1-insertion of the isonitrile carbon into a metal-acetylide bond, followed by a protonolysis by the acidic proton of the terminal alkyne. Additional insertion products were obtained by altering the catalyst and the reactant ratios. A plausible mechanism for the catalytic reaction is also presented, based on kinetics measurements and thermodynamic studies of the coupling reaction with Cp₂*ThMe₂ or [(Et₂N)₃U][BPh₄] as catalysts. The reaction is first-order in catalyst and isonitrile and zero-order in alkyne.

Original language	English
Pages (from-to)	3103-3112
Number of pages	10
Journal	Organometallics
Volume	27
Issue number	13
DOIs	https://doi.org/10.1021/om701223x
State	Published - 14 Jul 2008
Externally published	Yes

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title = "Coupling of terminal alkynes and isonitriles by organoactinide complexes: Scope and mechanistic insights",

abstract = "The coupling reaction of terminal alkynes with several isonitriles, catalyzed by the neutral organoactinide complexes Cp2*AnMe 2 (Cp* = C5Me5, An = Th, U) or the cationic complex [(Et2N)3U][BPh4], yielded substituted α,β-acetylenic aldimines, in good to excellent yields. The reaction proceeded via a 1,1-insertion of the isonitrile carbon into a metal-acetylide bond, followed by a protonolysis by the acidic proton of the terminal alkyne. Additional insertion products were obtained by altering the catalyst and the reactant ratios. A plausible mechanism for the catalytic reaction is also presented, based on kinetics measurements and thermodynamic studies of the coupling reaction with Cp2*ThMe2 or [(Et2N)3U][BPh4] as catalysts. The reaction is first-order in catalyst and isonitrile and zero-order in alkyne.",

author = "E. Barnea and T. Andrea and Berthet, {J. C.} and M. Ephritikhine and Eisen, {M. S.}",

year = "2008",

month = jul,

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doi = "10.1021/om701223x",

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journal = "Organometallics",

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TY - JOUR

T1 - Coupling of terminal alkynes and isonitriles by organoactinide complexes

T2 - Scope and mechanistic insights

AU - Barnea, E.

AU - Andrea, T.

AU - Berthet, J. C.

AU - Ephritikhine, M.

AU - Eisen, M. S.

PY - 2008/7/14

Y1 - 2008/7/14

N2 - The coupling reaction of terminal alkynes with several isonitriles, catalyzed by the neutral organoactinide complexes Cp2*AnMe 2 (Cp* = C5Me5, An = Th, U) or the cationic complex [(Et2N)3U][BPh4], yielded substituted α,β-acetylenic aldimines, in good to excellent yields. The reaction proceeded via a 1,1-insertion of the isonitrile carbon into a metal-acetylide bond, followed by a protonolysis by the acidic proton of the terminal alkyne. Additional insertion products were obtained by altering the catalyst and the reactant ratios. A plausible mechanism for the catalytic reaction is also presented, based on kinetics measurements and thermodynamic studies of the coupling reaction with Cp2*ThMe2 or [(Et2N)3U][BPh4] as catalysts. The reaction is first-order in catalyst and isonitrile and zero-order in alkyne.

AB - The coupling reaction of terminal alkynes with several isonitriles, catalyzed by the neutral organoactinide complexes Cp2*AnMe 2 (Cp* = C5Me5, An = Th, U) or the cationic complex [(Et2N)3U][BPh4], yielded substituted α,β-acetylenic aldimines, in good to excellent yields. The reaction proceeded via a 1,1-insertion of the isonitrile carbon into a metal-acetylide bond, followed by a protonolysis by the acidic proton of the terminal alkyne. Additional insertion products were obtained by altering the catalyst and the reactant ratios. A plausible mechanism for the catalytic reaction is also presented, based on kinetics measurements and thermodynamic studies of the coupling reaction with Cp2*ThMe2 or [(Et2N)3U][BPh4] as catalysts. The reaction is first-order in catalyst and isonitrile and zero-order in alkyne.

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U2 - 10.1021/om701223x

DO - 10.1021/om701223x

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SN - 0276-7333

VL - 27

SP - 3103

EP - 3112

JO - Organometallics

JF - Organometallics

IS - 13

ER -

Coupling of terminal alkynes and isonitriles by organoactinide complexes: Scope and mechanistic insights

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