ChemInform Abstract: Copper-Catalyzed N-tert-Butylation of Aromatic Amines under Mild Conditions Using tert-Butyl 2,2,2-Trichloroacetimidate (original) (raw)

Copper(II) catalyzed allylic amination of terpenic chlorides in water

Catalysis Communications, 2012

A highly efficient method for the synthesis of allylic amines from terpenic chlorides by cheap copper (II) as catalyst in water has been developed. Allylic chlorides react with high regioselectivity in the presence of secondary amines, under mild conditions to give N-allylic amines in excellent yields.

Copper-catalyzed N-arylation of amines with aryliodonium ylides in water

Beilstein Journal of Organic Chemistry

Copper sulfate catalyzed an efficient, inexpensive, and environment-friendly protocol that has been developed for N-arylation of amines with 1,3-cyclohexadione-derived aryliodonium ylides in water as a green solvent. Aromatic primary amines substituted with electron-donating as well as electron-withdrawing groups on the aryl ring reacted smoothly with iodonium ylides to give the corresponding diarylamines with good to excellent yields. Also, secondary amines underwent N-arylation to deliver tertiary amines with moderate yields.

Copper-Catalyzed Aliphatic C–H Amination with an Amidine Moiety

Organic Letters, 2013

A method for amination of aliphatic CÀH bonds of N-alkylamidines is described that utilizes Cu(OAc) 2 as the catalyst in the presence of PhI(OAc) 2 and K 3 PO 4. The resulting products, dihydroimidazoles and tetrahydropyrimidines, could be converted into the corresponding diamines by hydride reduction.

Copper-catalyzed decarboxylative coupling reactions for the synthesis of propargyl amines

When aryl alkynyl carboxylic acids were allowed to react with amines and aldehydes in CH 3 CN at 80°C in the presence of 10 mol % CuI, the desired propargyl amines were formed in good yields. This coupling reaction demonstrated to work across a broad range of reagents including functionalized aryl alkynyl carboxylic acids, aliphatic and aromatic aldehydes, and cyclic and acyclic amines.

Cu(II)-Mediated Ortho-C–H Amination of Arenes with Free Amines

Journal of Organic Chemistry, 2019

Copper-mediated direct ortho-C-H amination of arenes has been accomplished with the aid of easily removable bidentate pyridine N-oxide as a directing group. The use of free cyclic secondary amines and anilines as aminating agents and inexpensive copper acetate makes the strategy more effective and favorable from the economic point of view. This reaction is compatible with a wide range of functional groups to synthesize a variety of amine-containing products of high interest. This method also allows the short synthesis of central scaffold of pharmaceutically relevant Staphylococcus aureus Sortase A inhibitor.

Amination of aryl halides using copper catalysis

Tetrahedron Letters, 2001

Bromopyridine 4 was converted into aminopyridine 5 under Cu 2 O catalysis with an ethylene glycol solution of ammonia in excellent yield (90%). The amination reaction features low (0.5 mol%) catalyst loading, mild reaction temperature (80°C) and low reaction pressure (50 psi). This protocol is further studied in the amination of a variety of aryl halides.

On the Mechanism of Ligand-Assisted, Copper-Catalyzed Benzylic Amination by Chloramine-T

Organometallics, 2010

The mechanism of hydrocarbon amination by chloramine-T derivatives catalyzed by (diimine)copper complexes has been investigated. The initial synthetic study of the reactions revealed ligandaccelerated catalysis, significant sensitivity to the electronic character of the substrates, and low to moderate enantioselectivities with homochiral ligands. Various mechanistic probes, both experimental and computational, have been focused on the C-H insertion process. A kinetic isotope effect of 4.6 was found in the amination of R-D(H)-cumenes catalyzed by [(diimine)Cu(solv)]Z. Amination of the isomeric substrates cis-and trans-4-tert-butyl-1-phenylcyclohexanes with 4-Me-C 6 H 4 SO 2-NNaCl (chloramine-T) or 4-NO 2-C 6 H 4 SO 2 NNaCl (chloramine-N) catalyzed by [(diimine)Cu-(CH 3 CN)]PF 6 produced in all cases an approximately 1:1 mixture of the corresponding cis-and trans-4-tert-butyl-1-phenyl-1-sulfonaminocyclohexanes. Amination of the radical-clock substrate 1-phenyl-2-benzylcyclopropane with chloramine-T/(diimine)Cu(CH 3 CN)]PF 6 gave a mixture of ringopened and cyclopropylmethylamino derivatives. Together, these results are most consistent with a stepwise insertion of an N-Ts(Ns) unit into the C-H bond, via carbon radicals, and a secondary contribution from a concerted insertion pathway. B3LYP and CASSCF computations suggest that the C-H insertion step involves the reaction of the hydrocarbon with a Cu-imido (nitrene) complex, [(diimine)-CudNSO 2 R] þ. The ground-state triplet of the Cu-imido complex is calculated to be 3-13 kcal/mol more stable that the singlet complex, depending on the method and basis sets employed. The reaction of each complex with toluene is modeled to find that the C-H insertion transition state for the triplet (ΔG ‡ = 8.2 kcal/mol) is lower in energy than the singlet. The former reacts by a stepwise H-atom abstraction, while the latter reacts by a concerted C-H insertion. These results and kinetic isotope effect calculations for the singlet (2.9) and triplet (4.8) pathways, respectively, agree with the experimental observations (4.6) and point to a major role for the triplet complex in the stepwise, nonstereoselective insertion pathway.