A metal π-Lewis base activation model for Pd-catalyzed hydroamination of amines and 1,3-dienes
Xiao Yan, Xiuming Yang, Peng Yan, Bo Zhao, Rong Zeng, Bin Pan, Ying‐Chun Chen, Lei Zhu, Qin Ouyang
Abstract
π-Lewis base activation, which undergoes protonation with a variety of acidic sources, such as Brønsted acids, Lewis acid-activated indazoles, and Pd(ii) pre-catalyst triggered ammonium salts. The resultant π-allyl palladium complexes undergo the amination reaction to give the final observed products. FMO and NPA analyses have revealed the nature of Pd(0) mediated π-Lewis base activation of 1,3-dienes. The calculation results show that the π-Lewis base activation pathway is more favourable than the Pd(ii)-H species involved one in different reactions. Further control experiments corroborated our mechanistic proposal, and an efficient Pd(0) mediated hydroamination reaction was developed.