150432-17-0Relevant articles and documents
A nickel-catalyzed route to pyridines
McCormick, Michael M.,Duong, Hung A.,Zuo, Gang,Louie, Janis
, p. 5030 - 5031 (2005)
A mild and general route for preparing pyridines from nitriles and diynes is described. Ni/imidazolyidene complexes were used to mediate cyclization alkynes and both aryl and alkyl nitriles at ambient temperature. In addition, the efficacy of this protoco
DFT studies on the reaction mechanisms of 1,4-dilithio 1,3-dienes with nitriles
Zhao, Fei,Zhan, Ming,Zhang, Wen-Xiong,Xi, Zhenfeng
, p. 2059 - 2068 (2013/05/21)
Mechanisms for the reactions of 1,4-dilithio-1,3-butadienes and nitriles are explored through both experiments and DFT calculations. The computational results suggest that the selectivity of these reaction systems is strongly affected by the structures of the substrates. As the first step of all reaction pathways, the addition intermediate of one C-Li bond to the nitrile is formed. When tetraalkyl-substituted 1,4-dilithio 1,3-dienes and 2-cyanopyridine are used, the intermediate gives the cyclopentadienyl amine product as the kinetic product because of the coordination of the pyridyl N atom to the lithium atoms (system B). This addition intermediate also undergoes a second nitrile insertion into the C-Li bond, giving the dilithio ketimine intermediate. When tetraalkyl-substituted 1,4-dilithio 1,3-dienes and aryl nitriles are used, the dilithio ketimine intermediate undergoes a 1,6-cyclization, generating pyridine and triazine products through thermodynamically favored pathways (systems A and B). When cyclic 1,4-dilithiobutadiene and tertiary aliphatic nitriles are used, the dilithio ketimine intermediate undergoes two sequential 1,5-cyclization steps with a lower energy barrier, generating tricyclic Δ1- bipyrrolines (system C). Experimentally, the lithium-containing triazine intermediate 10 and Δ1-bipyrroline intermediate 19 have been isolated and their structures investigated through NMR and quenching experiments. The calculation results clearly show the mechanism details of these reactions and are in good agreement with the experimental observations.
Highly efficient synthesis of stereodefined multisubstituted 1,4-dicyano-and 1-cyano-1,3-butadienes and their reactions with organolithium reagents
Wang, Congyang,Wang, Chao,Wang, Qifeng,Wang, Zhihui,Sun, Hui,Guo, Xiangyu,Xi, Zhenfeng
, p. 6484 - 6494 (2008/02/13)
Stereodefined multisubstituted 1-cyano- and 1,4-dicyano-1,3-butadiene derivatives were obtained in excellent yields of the isolated product from their corresponding monohalo-and dihalobutadienes and CuCN. This reaction proceeded with high stereose-lectivi
