Two Copper-Carbenes from One Diazo Compound
Álvarez, María (Universidad de Huelva)
Besora, Maria (Universitat Rovira i Virgili)
Molina, Francisco (Universidad de Huelva)
Maseras Cuní, Feliu (Universitat Autònoma de Barcelona. Departament de Química)
Belderrain, Tomás R. (Universidad de Huelva)
Pérez, Pedro J. (Universidad de Huelva)

Date:	2021
Abstract:	Many transition-metal complexes ML decompose diazo compounds N=CR 1 R 2 generating metal-carbenes LM=CR 1 R 2 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the CR 1 R 2 fragment at the metal-carbene remains intact from the parent diazo compound. Herein we report the detection and isolation of a monosubstituted copper carbene where the CR 1 R 2 ligand has undergone a modification from the initial diazo reagent. When Tp Ms Cu(THF) (Tp Ms = hydrotris(3-mesityl)pyrazolylborate ligand) was reacted with N,N -diethyl diazoacetamide [N=C(H)(CONEt)], the stable copper carbene Tp Ms Cu=C(H)(NEt) was isolated, resulting from a decarbonylation process, with carbon monoxide being trapped as Tp Ms Cu(CO). The simultaneous observation of products derived from the intramolecular carbene insertion reaction into C-H bonds demonstrates that the expected Tp Ms Cu=C(H)(CONEt) complex is also formed. Experimental data, DFT calculations, and microkinetic models allow us to propose that the latter undergoes CO loss en route to the former.
Grants:	Agencia Estatal de Investigación CTQ2017-87792-R Agencia Estatal de Investigación CTQ2017-82893-C2-1-R Ministerio de Economía y Competitividad CTQ2016-81923-REDC
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Published in:	Journal of the American Chemical Society, Vol. 143 (March 2021) , p. 4837-4843, ISSN 1520-5126

DOI: 10.1021/jacs.1c01483
PMID: 33733762

7 p, 2.1 MB

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