- Heck reaction with heteroaryl halides in the presence of a palladium-tetraphosphine catalyst
-
cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/1/2[PdCl (C3H5)]2 system catalyses efficiently the Heck reaction of heteroaryl halides with n-butyl acrylate, styrene, vinylpyridine and vinyl ether derivatives. High turnover numbers can be obtained for the reactions with halo pyridines, quinolines, furans or thiophenes.
- Berthiol, Florian,Feuerstein, Marie,Doucet, Henri,Santelli, Maurice
-
-
Read Online
- Role of mono-N-protected amino acid ligands in palladium(II)-catalyzed dehydrogenative heck reactions of electron-deficient (hetero)arenes: Experimental and computational studies
-
We report here that mono-N-protected amino acids (MPAAs), an important environmentally compatible structural motif, enable acceleration of Pd(II)-catalyzed dehydrogenative Heck reactions between pyridines and electron-deficient arenes with simple alkenes, leading to diversely functionalized C3- or meta-selective alkenylated pyridines and benzenes via non-chelate-assisted C-H activation. A comprehensive theoretical study by DFT calculations discloses that the amino scaffold of the MPAA ligand facilely converts to an X-type ligand by an initial N-H activation, resulting in a relatively low activation barrier for the C-H cleavage of pyridine. Then a property reversal of the amino group from X-type to L-type ligand allows the alkene substitution to take place smoothly, while the carboxyl group enables the formation of an intramolecular hydrogen bond, significantly decreasing the activation barrier for the carbopalladation. The results of calculations and the kinetic isotopic effect measurement support a rate-limiting C-H activation by a mechanism involving a concerted metalation/deprotonation pathway, with an endothermicity of 31.0 kcal/mol in the process.
- Cong, Xuefeng,Tang, Huarong,Wu, Chao,Zeng, Xiaoming
-
-
Read Online
- Regiospecific [2+2] photocycloadditions of an unsymmetrical olefin in the solid state based on metal-mediated assemblies
-
An unsymmetrical olefin in two coordination polymers underwent solid state [2+2] photocycloaddition reactions resulting in quantitative yields. The reactions afforded the head-to-head and head-to-tail photodimer isomers of cyclobutane derivatives with abs
- Chen, Jing-Min,Hou, Yi-Xuan,Zhou, Qian-Kun,Zhang, Hao,Liu, Dong
-
-
Read Online