Facile Synthesis of Chiral Arylamines, Alkylamines and Amides by Enantioselective NiH-Catalyzed Hydroamination

Published on Aug 27, 2021in Angewandte Chemie12.959
· DOI :10.1002/ANIE.202109881
Lingpu Meng (NU: Nanjing University), Jingjie Yang (NU: Nanjing University)+ 2 AuthorsShaolin Zhu20
Estimated H-index: 20
(NU: Nanjing University)
Regio- and enantioselective hydroarylamination, hydroalkylamination and hydroamidation of styrenes have been developed by NiH catalysis with a simple bioxazoline ligand under mild conditions. A wide range of enantioenriched benzylic arylamines, alkylamines and amides can be easily accessed by nitroarenes, hydroxylamines and dioxazolones, respectively as amination reagents. The chiral induction in these reactions is proposed to proceed through an enantiodifferentiating syn-hydronickellation step.
📖 Papers frequently viewed together
1 Author (Kevin D. Hesp)
27 Citations
134 Citations
3 Authors (Fang Xie, ..., Xingwei Li)
30 Citations
#1Jian Chen (NU: Nanjing University)H-Index: 4
#2Shaolin Zhu (NU: Nanjing University)H-Index: 20
A nickel-catalyzed, multicomponent regio- and enantioselective coupling via sequential hydroformylation and carbonylation from readily available starting materials has been developed. This modular multicomponent hydrofunctionalization strategy enables the straightforward reductive hydrocarbonylation of a broad range of unactivated alkenes to produce a wide variety of unsymmetrical dialkyl ketones bearing a functionalized α-stereocenter, including enantioenriched chiral α-aryl ketones and α-amino...
1 CitationsSource
#1Fang Zhou (NU: Nanjing University)
#2Shaolin Zhu (NU: Nanjing University)H-Index: 20
4 CitationsSource
#6You Wang (NU: Nanjing University)H-Index: 6
α-Chiral alkyne is a key structural element of many bioactive compounds, chemical probes, and functional materials, and is a valuable synthon in organic synthesis. Here we report a NiH-catalysed reductive migratory hydroalkynylation of olefins with bromoalkynes that delivers the corresponding benzylic alkynylation products in high yields with excellent regioselectivities. Catalytic enantioselective hydroalkynylation of styrenes has also been realized using a simple chiral PyrOx ligand. The obtai...
4 CitationsSource
#1Yang Gao (GDUT: Guangdong University of Technology)H-Index: 12
#2Simin Yang (GDUT: Guangdong University of Technology)H-Index: 2
Last. Xiao-Qiang Hu (SCUN/SCUEC: South Central University for Nationalities)H-Index: 18
view all 6 authors...
4 CitationsSource
#1Shan Wang (Southern University of Science and Technology)H-Index: 1
#2Jian-Xin Zhang (Southern University of Science and Technology)H-Index: 1
Last. Wei Shu (Southern University of Science and Technology)H-Index: 28
view all 6 authors...
Chiral aliphatic amine and alcohol derivatives are ubiquitous in pharmaceuticals, pesticides, natural products and fine chemicals, yet difficult to access due to the challenge to differentiate between the spatially and electronically similar alkyl groups. Herein, we report a nickel-catalyzed enantioselective hydroalkylation of acyl enamines and enol esters with alkyl halides to afford enantioenriched α-branched aliphatic acyl amines and esters in good yields with excellent levels of enantioselec...
9 CitationsSource
#1Xiang LyuH-Index: 1
#2Jianbo ZhangH-Index: 4
Last. Sukbok ChangH-Index: 90
view all 5 authors...
The formal hydroamination/hydroamidation utilizing metal hydride is an appealing synthetic tool for the construction of valuable nitrogen-containing compounds from unsaturated hydrocarbons. While significant advances have been made for the functionalizations of alkenes in this realm, the direct hydroamidation of alkynes remains rather limited due to the high feasibility of the key metal-alkenyl intermediate to choose other reaction pathways. Herein, we report a NiH-catalyzed strategy for the hyd...
5 CitationsSource
#1Xiao-Xu Wang (USTC: University of Science and Technology of China)H-Index: 5
#2Lu Yu (CAS: Chinese Academy of Sciences)H-Index: 2
Last. Yao Fu (USTC: University of Science and Technology of China)H-Index: 58
view all 7 authors...
Chiral dialkyl carbinols and their derivatives are significant synthetic building blocks in organic chemistry and related fields. The development of convenient and efficient methods to access these...
3 CitationsSource
#1Srikrishna Bera (EPFL: École Polytechnique Fédérale de Lausanne)H-Index: 8
#2Run-Ze Mao (EPFL: École Polytechnique Fédérale de Lausanne)H-Index: 10
Last. Xile Hu (EPFL: École Polytechnique Fédérale de Lausanne)H-Index: 76
view all 3 authors...
Cross-coupling of two alkyl fragments is an efficient method to produce organic molecules rich in sp3-hybridized carbon centres, which are attractive candidate compounds in drug discovery. Enantioselective C(sp3)-C(sp3) coupling is challenging, especially of alkyl electrophiles without an activating group (aryl, vinyl, carbonyl). Here, we report a strategy based on nickel hydride addition to internal olefins followed by nickel-catalysed alkyl-alkyl coupling. This strategy enables the enantiosele...
19 CitationsSource
#1Jia-Wang Wang (USTC: University of Science and Technology of China)H-Index: 3
#2Yan Li (USTC: University of Science and Technology of China)H-Index: 86
Last. Yao Fu (USTC: University of Science and Technology of China)H-Index: 58
view all 8 authors...
To increase the reliability and success rate of drug discovery, efforts have been made to increase the C(sp3) fraction and avoid flat molecules. sp3-Rich enantiopure amines are most frequently encountered as chiral auxiliaries, synthetic intermediates for pharmaceutical agents and bioactive natural products. Streamlined construction of chiral aliphatic amines has long been regarded as a paramount challenge. Mainstream approaches, including hydrogenation of enamines and imines, C-H amination, and...
13 CitationsSource
#1Jiandong Liu (SHU: Shanghai University)H-Index: 1
#2Hegui Gong (SHU: Shanghai University)H-Index: 22
Last. Shaolin Zhu (NU: Nanjing University)H-Index: 20
view all 3 authors...
A NiH-catalyzed migratory hydroalkenylation reaction of olefins with alkenyl bromides has been developed, affording benzylic alkenylation products with high yields and excellent chemoselectivity. The mild conditions of the reaction preclude olefinic products from undergoing further isomerization or subsequent alkenylation. Catalytic enantioselective hydroalkenylation of styrenes was achieved by using a chiral bisoxazoline ligand.
15 CitationsSource
Cited By1