20155-68-4Relevant articles and documents
Two Copper-Carbenes from One Diazo Compound
álvarez, María,Besora, Maria,Molina, Francisco,Maseras, Feliu,Belderrain, Tomás R.,Pérez, Pedro J.
, p. 4837 - 4843 (2021)
Many transition-metal complexes MLn decompose diazo compounds N2=CR1R2 generating metal-carbenes LnM=CR1R2 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the CR1R2 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 CR1R2 ligand has undergone a modification from the initial diazo reagent. When TpMsCu(THF) (TpMs = hydrotris(3-mesityl)pyrazolylborate ligand) was reacted with N,N-diethyl diazoacetamide [N2=C(H)(CONEt2)], the stable copper carbene TpMsCu=C(H)(NEt2) was isolated, resulting from a decarbonylation process, with carbon monoxide being trapped as TpMsCu(CO). The simultaneous observation of products derived from the intramolecular carbene insertion reaction into C-H bonds demonstrates that the expected TpMsCu=C(H)(CONEt2) 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.
A New Synthetic Route to 2-Dialkylamino-2-alkenals
Keiko, N. A.,Rulev, A. Yu.,Kalikhman, I. D.,Voronkov, M. G.
, p. 446 - 447 (2007/10/02)
2-Dialkylamino-2-alkenals are easily prepared by reaction of 2-halo-2-alkenals with secondary aliphatic amines.
