90408-21-2Relevant articles and documents
Atom Transfer Radical Polymerization-Inspired Room Temperature (sp3)C-N Coupling
Coote, Michelle L.,Fung, Alfred. K. K.,Sherburn, Michael S.,Yu, Li-Juan
, p. 9723 - 9732 (2021/07/20)
A simple nonphotochemical procedure is reported for Cu(I)-catalyzed C-N coupling of aliphatic halides with amines and amides. The process is loosely based on the Goldberg reaction but takes place readily at room temperature. It uses Cu(I)Br, a commonly used and inexpensive atom transfer radical polymerization precatalyst, along with the cheap ligand N,N,N′,N″,N″-pentamethyldiethylenetriamine, to activate the R-X bond of the substrate via inner-sphere electron transfer. The procedure brings about productive C-N bond formation between a range of alkyl halide substrates with heterocyclic aromatic amines and amides. The mechanism of the coupling step, which was elucidated through application of computational methods, proceeds via a unique Cu(I) → Cu(II) → Cu(III) → Cu(I) catalytic cycle, involving (a) inner-sphere electron transfer from Cu(I) to the alkyl halide to generate the alkyl radical; (b) successive coordination of the N-nucleophile and the radical to Cu(II); and finally reductive elimination. In the absence of a nucleophile, debrominative homocoupling of the alkyl halide occurs. Control experiments rule out SN-type mechanisms for C-N bond formation.
Lithiation of 1-Benzylimidazole. A Hypothesis on the Regioselectivity of the Electrophilic Attacks on the Lithiated Species
Moreno-Manas, M.,Bassa, J.,Llado, N.,Pleixats, R.
, p. 673 - 678 (2007/10/02)
Sequential lithiations of 1-benzylimidazole, 1, and of 1-benzyl-1,2,4-triazole,2, followed by treatment with electrophiles others than alkyl halides result in reactions at C-2.However, benzyl halides and, to a certain extent, iodomethane react at the N-benzyl carbon atom.An explanatory hypothesis based on steric ortho effects is advanced.
