Additive-Free Transfer Hydrogenative Direct Asymmetric Reductive Amination Using a Chiral Pyridine-Derived Half-Sandwich Catalyst
|Corresponding Author||Xu，Liang; Li，Pengfei|
Chiral amines are broadly used compounds in pharmaceutical industry and organic synthesis, and reductive amination reactions have been the most appreciated methods for their syntheses. However, one-step transfer hydrogenative direct asymmetric reductive amination (THDARA) that could expand the scope, simplify the operation and eliminate the use of additives has been challenging. In this work, based on the Xiao's racemic transfer hydrogenative reductive amination in 2010 and our recent work in novel chiral pyridine ligands, chiral half-sandwich iridium catalysts were rationally designed and synthesized. Using the optimized catalyst and azeotropic mixture of formic acid and triethylamine as the hydrogen source, a broad range of α-chiral (hetero)aryl amines, including various polar functional groups and heterocycles, were prepared in generally high yield and enantioselectivity under mild and operationally simple conditions. Density functional theory (DFT) calculation of the catalytically active Ir−H species and the key hydride transfer step supported the chiral pyridine-induced stereospecific generation of the iridium center, and the enantioselection by taming the highly flexible key transition structure with multiple attractive non-covalent interactions. This work introduced a type of effective chiral catalysts for simplified approach to medicinally important chiral amines, as well as a rare example of robust enantioselective transition-metal catalysis.
NI Journal Papers
Guangdong Provincial Key Laboratory Of Catalysis[2020B121201002];Natural Science Basic Research Program of Shaanxi Province[2020JC-08];National Natural Science Foundation of China;National Natural Science Foundation of China;National Natural Science Foundation of China;National Postdoctoral Program for Innovative Talents[BX20220252];Fundamental Research Funds for the Central Universities[xtr072022003];
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Cited Times [WOS]:0
|Document Type||Journal Article|
1.Frontier Institute of Science and Technology,Xi'an Jiaotong University,Xi'an,Shaanxi,710054,China
2.School of Chemistry and Chemical Engineering/Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan,Shihezi University,Shihezi,Xinjiang,832003,China
3.Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China
4.Key Laboratory of Applied Surface and Colloid Chemistry,Ministry of Education/School of Chemistry and Chemical Engineering,Shaanxi Normal University,Xi'an,Shaanxi,710062,China
5.School of Chemistry,Xi'an Jiaotong University,Xi'an,Shaanxi,710049,China
|First Author Affilication||Southern University of Science and Technology|
|Corresponding Author Affilication||Southern University of Science and Technology|
Gao，Yuan,Wang，Zhijun,Zhang，Xinyu,et al. Additive-Free Transfer Hydrogenative Direct Asymmetric Reductive Amination Using a Chiral Pyridine-Derived Half-Sandwich Catalyst[J]. Angewandte Chemie - International Edition,2023,62(31).
Gao，Yuan.,Wang，Zhijun.,Zhang，Xinyu.,Zhao，Min.,Zhang，Shuai.,...&Li，Pengfei.(2023).Additive-Free Transfer Hydrogenative Direct Asymmetric Reductive Amination Using a Chiral Pyridine-Derived Half-Sandwich Catalyst.Angewandte Chemie - International Edition,62(31).
Gao，Yuan,et al."Additive-Free Transfer Hydrogenative Direct Asymmetric Reductive Amination Using a Chiral Pyridine-Derived Half-Sandwich Catalyst".Angewandte Chemie - International Edition 62.31(2023).
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