A metal p-Lewis base activation model for Pd-catalyzed hydroamination of amines and 1,3-dienes

被引：14

作者：

Yan, Xiao ^{[1
]}

Yang, Xiu-Ming ^{[1
]}

Yan, Peng ^{[1
]}

Zhao, Bo ^{[1
]}

Zeng, Rong ^{[1
]}

Pan, Bin ^{[1
]}

Chen, Ying-Chun ^{[1
,2
]}

Zhu, Lei ^{[1
]}

Ouyang, Qin ^{[1
]}

机构：

[1] Third Mil Med Univ, Coll Pharm, Chongqing 400038, Peoples R China

[2] Sichuan Univ, Sichuan Res Ctr Drug Precis Ind Technol, West China Sch Pharm, Key Lab Drug Targeting & Drug Delivery Syst,Minist, Chengdu 610041, Peoples R China

来源：

CHEMICAL SCIENCE | 2023年 / 14卷 / 17期

基金：

国家重点研发计划;

关键词：

SOLVATION FREE-ENERGIES; INTERMOLECULAR HYDROAMINATION; ASYMMETRIC HYDROAMINATION; COMPLEX; ALKENES; DIENES; REGIOSELECTIVITY; AMINATION; MECHANISM; ANILINES;

D O I：

10.1039/d2sc05835a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

As a general mechanism proposal, a Pd(ii)-H migration insertion process is not able to well explicate the Pd-catalyzed hydroamination of amines and 1,3-dienes. Here we demonstrate that 1,3-dienes form electron-neutral and HOMO-raised ?(2)-complexes with Pd(0) via p-Lewis base activation, which undergoes protonation with a variety of acidic sources, such as Bronsted acids, Lewis acid-activated indazoles, and Pd(ii) pre-catalyst triggered ammonium salts. The resultant p-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 p-Lewis base activation of 1,3-dienes. The calculation results show that the p-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.

引用

页码：4597 / 4604

页数：8

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