The development of new amine–amide ligands for application in Cu(II)-catalyzed enantioselective Henry reactions. Issue 13 (15th July 2016)

• Record Type: Journal Article
• Authors: Ao, Chunyan; Men, Jian; Wang, Yang; Shao, Tao; Huang, Yuanyuan; Huo, Junji; Gao, Guowei
• Is Part Of: Tetrahedron, asymmetry. Volume 27:Issue 13(2016)
• Page Start: 589
• Page End: 595
• Publication Date: 2016-07-15
• Subjects: Asymmetry (Chemistry) -- Periodicals; 547.005
• DOI: 10.1016/j.tetasy.2016.05.005
• Languages: English
• ISSNs: 0957-4166

Abstract

Graphical abstract: Abstract: A new type of chiral tertiary amine ligand was designed and derived froml -proline and ( R )-BINOL. These new chiral ligands chelated with Cu(II) showed highly catalytic efficiency in enantioselective Henry reactions. Excellent yields (up to 99%) and high enantioselectivities (up to 96% ee) were achieved for aromatic, hetero-aromatic and aliphatic aldehyde substrates, without an additional base additive or the need for air or moisture exclusion. Abstract : ( S )-1-(2-(( R )-3 H -Dinaphtho[2, 1-c:1′, 2′-e]azepin-4(5 H )-yl)ethyl)- N -butylpyrrolidine-2-carboxamide: C33 H37 N3 O [ α ]D 25 = −248.0 ( c 0.51, CH2 Cl2 ) Absolute configuration: ( S, R ) Abstract : ( S )-1-(2-(( R )-3 H -Dinaphtho[2, 1-c:1′, 2′-e]azepin-4(5 H )-yl)ethyl)- N -( tert -butyl)pyrrolidine-2-carboxamide: C33 H37 N3 O [ α ]D 25 = −222.8 ( c 0.5, CH2 Cl2 ) Absolute configuration: ( S, R ) Abstract : ( S )-1-(2-(( R )-3 H -Dinaphtho[2, 1-c:1′, 2′-e]azepin-4(5 H )-yl)ethyl)- N -cyclohexylpyrrolidine-2-carboxamide: C35 H39 N3 O [ α ]D 25 = −229.4 ( c 0.5, CH2 Cl2 ) Absolute configuration: ( S, R ) Abstract : ( S )-1-(2-(( R )-3 H -Dinaphtho[2, 1-c:1′, 2′-e]azepin-4(5 H )-yl)ethyl)- N -phenylpyrrolidine-2-carboxamide: C35 H33 N3 O [ α ]D 25 = −297.4 ( c 0.5, CH2 Cl2 ) Absolute configuration: ( S, R ) Abstract : ( S )-1-(2-(( R )-3 H -Dinaphtho[2, 1-c:1′, 2′-e]azepin-4(5 H )-yl)ethyl)- N -(naphthalen-1-yl)pyrrolidine-2-carboxamide: C39 H36 N3 O [ α ]D 31 = 239.0 ( c 0.51, CH2 Cl2 ) Absolute configuration: ( S, R ) Abstract : ( R )-4-(2-(Pyrrolidin-1-yl)ethyl)-4, 5-dihydro-3 H -dinaphtho[2, 1-c:1′, 2′-e]azepine: C28 H28 N2 [ α ]D 25 = +63.7 ( c 0.19, CH2 Cl2 ) Absolute configuration: ( R ) Abstract : ( S )-1-(2-(Isoindolin-2-yl)ethyl)- N -(naphthalen-1-yl)pyrrolidine-2-carboxamide: C25 H28 N3 O [ α ]D 25 = −79.4 ( c 0.51, CH2 Cl2 ) Absolute configuration: ( R )