Additive-Free Transfer Hydrogenative Direct Asymmetric Reductive Amination Using a Chiral Pyridine-Derived Half-Sandwich Catalyst

Gao，Yuan1,3; Wang，Zhijun2; Zhang，Xinyu2; Zhao，Min1; Zhang，Shuai1; Wang，Chao4; Xu，Liang2; Li，Pengfei1,3,5

2023-08-01

10.1002/anie.202303709

Angewandte Chemie - International Edition   影响因子和分区

1433-7851

1521-3773

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.

Asymmetric Catalysis Chiral Pyridine Half-Sandwich Catalyst Non-Covalent Interaction Reductive Amination

SCI ; EI

英语

通讯

Guangdong Provincial Key Laboratory Of Catalysis[2020B121201002];Natural Science Basic Research Program of Shaanxi Province[2020JC-08];National Natural Science Foundation of China[21963010];National Natural Science Foundation of China[21971202];National Natural Science Foundation of China[22171218];National Postdoctoral Program for Innovative Talents[BX20220252];Fundamental Research Funds for the Central Universities[xtr072022003];

Chemistry

Chemistry, Multidisciplinary

WOS:001016087200001

WILEY-V C H VERLAG GMBH

20232614311928

Additives ; Amines ; Catalysis ; Density functional theory ; Enantioselectivity ; Iridium ; Pyridine ; Synthesis (chemical)

Precious Metals:547.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

CHEMISTRY

2-s2.0-85162942910

Scopus

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

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).