15429-18-2Relevant articles and documents
Addition of diethylzinc to imines promoted by Lewis acid
Hou, Xue Long,Zheng, Xiao Lan,Dai, Li Xin
, p. 6949 - 6952 (1998)
The alkylation of imines by using diethylzinc reagent in the presence of Lewis acid afforded secondary amines in high yield.
Iridium-Catalyzed Reductive Alkylations of Secondary Amides
Ou, Wei,Han, Feng,Hu, Xiu-Ning,Chen, Hang,Huang, Pei-Qiang
supporting information, p. 11354 - 11358 (2018/08/28)
Reported herein is the first direct, metal-catalyzed reductive functionalization of secondary amides to give functionalized amines and heterocycles. The method is shown to have exceptionally broad scope with respect to suitable nucleophiles, which cover both hard and soft C nucleophiles as well as a P nucleophile. The reaction exhibits good chemoselectivity and tolerates several sensitive functional groups.
An (Aminopyrimidinato)titanium catalyst for the hydroamination of alkynes and alkenes
Brahms, Christian,Tholen, Patrik,Saak, Wolfgang,Doye, Sven
, p. 7583 - 7592 (2013/12/04)
A new (aminopyrimidinato)titanium complex has been synthesised from inexpensive and easily accessible 2-(tert-butylamino)pyrimidine and [Ti(NMe 2)4] and used as a catalyst for the intermolecular hydroamination of alkynes as well as the cyclization of aminoalkenes. The hydroamination reactions of 1-phenylpropyne and terminal arylalkynes deliver the corresponding anti-Markovnikov addition products with excellent yields and regioselectivities. A new (aminopyrimidinato)titanium complex has been synthesised from inexpensive 2-(tert-butylamino)pyrimidine and [Ti(NMe 2)4] and used as a catalyst for the intermolecular hydroamination of alkynes as well as the cyclization of aminoalkenes. The complex represents the first example of a catalyst for the hydroamination of alkynes that contains an aminoheteroaromatic ancillary ligand.
[Ind2TiMe2]: A general catalyst for the intermolecular hydroamination of alkynes
Heutling, Andreas,Pohlki, Frauke,Doye, Sven
, p. 3059 - 3071 (2007/10/03)
[Ind2TiMe2] (Ind=indenyl) is a highly active and general catalyst for the intermolecular hydroamination of alkynes. It catalyzes the reaction of primary aryl-, tert-alkyl-, sec-alkyl-, and nalkylamines with internal and terminal alkynes. In the case of unsymmetrically substituted 1-phenyl-2-alkylalkynes, the reactions occur with modest to excellent regioselectivities, whereby formation of the anti-Markovnikov regioisomers is favored. While the major product of hydroamination reactions of terminal arylalkynes is always the anti-Markovnikov isomer, alkylalkynes react with arylamines to preferably give the Markovnikov products. To achieve reasonable rates for the addition of sterically less hindered n-alkyland benzylamines to alkynes, these amines must be added slowly to the reaction mixtures. This behavior is explained by the fact that the catalytic cycle proposed on the basis of an initial kinetic investigation includes the possibility that the rate of the reaction increases with decreasing concentration of the employed amine. Furthermore, no dimerization of the catalytically active imido complex is observed in the hydroamination of 1-phenylpropyne with 4-methylaniline in the presence of [Ind2TiMe2] as catalyst. In general, a combination of [Ind2TiMe2]-catalyzed hydroamination of alkynes with subsequent reduction leads to the formation of secondary amines with good to excellent yields. Particularly impressive is that [Ind 2TiMe2] makes it possible for the first time to perform the reactions of n-alkyl- and benzylamines with 1-phenylpropyne in a highly regioselective fashion.
