Synthesis and catalytic application of ferrocene substituted camphane-based aminoalcohols and S-containing heterocyclic analogues. Issue 17 (1st October 2016)

• Record Type: Journal Article
• Authors: Kamenova-Nacheva, Mariana; Dobrikov, Georgi M.; Dimitrov, Vladimir
• Is Part Of: Tetrahedron, asymmetry. Volume 27:Issue 17/18(2016)
• Page Start: 852
• Page End: 864
• Publication Date: 2016-10-01
• Subjects: Asymmetry (Chemistry) -- Periodicals; 547.005
• DOI: 10.1016/j.tetasy.2016.07.012
• Languages: English
• ISSNs: 0957-4166

Abstract

Graphical abstract: Abstract: A facile and practical approach was developed for the synthesis of chiral α-, β- and δ-aminoalcohols and S -containing heterocyclic analogues by using of readily available sources of chirality. The synthetic strategy involves utilization of camphor-derived ferrocene-containing starting compounds allowing, by means of nucleophilic additions of functionalized organolithiums, for the preparation of a small library of structurally diverse multifunctional derivatives possessing the bicyclic camphane skeleton as the central core. The new diastereoisomeric pure aminoalcohols and S -containing heterocyclic analogues have been evaluated as precatalysts for the addition of diethyl zinc to benzaldehyde providing in some cases very high enantioselectivity (up to 96%). Abstract : (1 R, 2 R, 4S, E )-3-(Ferrocenylmethylidene)-2-(2-(dimethylamino)phenyl)-1, 7, 7-trimethylbicyclo[2.2.1]heptan-2-ol: C29 H35 FeNO [ α ]D 20 = −136.9 ( c 0.41, CHCl3 ) Source of chirality: (1 R )-(+)-camphor Absolute configuration: (1 R, 2 R, 4S, E ) Abstract : (1 R, 2 R, 4 S, E )-3-(Ferrocenylmethylidene)-2-(2-((dimethylamino)methyl)-3-(trimethylsilyl)phenyl)-1, 7, 7-trimethylbicyclo[2.2.1]heptan-2-ol: C33 H45 FeNOSi [ α ]D 20 = −381.8 ( c 0.40, CHCl3 ) Source of chirality: (1 R )-(+)-camphor Absolute configuration: (1 R, 2 R, 4 S, E ) Abstract : (1 R, 2 R, 4 S, E )-3-(Ferrocenylmethylidene)-2-(2-((dimethylamino)methyl)phenyl)-1, 7, 7-trimethylbicyclo[2.2.1]heptan-2-ol: C30 H37 FeNO [ α ]D 20 = −389.7 ( c 1.00, CHCl3 ) Source of chirality: (1 R )-(+)-camphor Absolute configuration: (1 R, 2 R, 4 S, E ) Abstract : (1 R, 2 R, 4 S, E )-3-(Ferrocenylmethylidene)-2-(3-(dimethylamino)propyl)-1, 7, 7-trimethylbicyclo[2.2.1]heptan-2-ol: C26 H37 FeNO [ α ]D 20 = −31.0 ( c 0.58, CHCl3 ) Source of chirality: (1 R )-(+)-camphor Absolute configuration: (1 R, 2 R, 4 S, E ) Abstract : (1 R, 2 R, 4 S, E )-3-(Ferrocenylmethylidene)-1, 7, 7-trimethyl-2-(thiophen-2-yl)bicyclo[2.2.1]heptan-2-ol: C25 H28 FeOS [ α ]D 20 = −261.0 ( c 1.29, hexane) Source of chirality: (1 R )-(+)-camphor Absolute configuration: (1 R, 2 R, 4 S, E ) Abstract : 1-((1 S, 2 R, 4 S, E )-3-(Ferrocenylmethylidene)-2-(3-(dimethylamino)propyl)-2-hydroxy-7, 7-dimethylbicyclo[2.2.1]heptan-1-yl)- N, N -dimethylmethanesulfonamide: C28 H42 FeN2 O3 S [ α ]D 20 = −68.3 ( c 0.38, CHCl3 ) Source of chirality: (1 S )-(+)-camphor-10-sulfonyl chloride Absolute configuration: (1 S, 2 R, 4 S, E ) Abstract : 1-((1 S, 2 R, 4 S, E )-3-Ferrocenylmethylidene-2-hydroxy-2-(1-isopropyl-1 H -imidazol-2-yl)-7, 7-dimethylbicyclo[2.2.1]heptan-1-yl)- N, N -dimethylmethanesulfonamide: C29 H39 FeN3 O3 S [ α ]D 20 = −339.0 ( c 0.64, CHCl3 ) Source of chirality: (1 S )-(+)-camphor-10-sulfonyl chloride Absolute configuration: (1 S, 2 R, 4 S, E ) Abstract : 1-((1 S, 2 R, 4 S, E )-2-(Benzo[ b ]thiophen-2-yl)-3-ferrocenylmethylidene-2-hydroxy-7, 7-dimethylbicyclo[2.2.1]heptan-1-yl)- N, N -dimethylmethanesulfonamide: C31 H35 FeNO3 S2 [ α ]D 20 = −256.3 ( c 1.00, CHCl3 ) Source of chirality: (1 S )-(+)-camphor-10-sulfonyl chloride Absolute configuration: (1 S, 2 R, 4 S, E ) Abstract : 1-((1 S, 2 R, 4 S, E )-3-Ferrocenylmethylidene-2-(dibenzo[ b, d ]thiophen-4-yl)-2-hydroxy-7, 7-dimethylbicyclo[2.2.1]heptan-1-yl)- N, N -dimethylmethanesulfonamide: C35 H37 FeNO3 S2 [ α ]D 20 = −216.2 ( c 0.63, CHCl3 ) Source of chirality: (1 S )-(+)-camphor-10-sulfonyl chloride Absolute configuration: (1 S, 2 R, 4 S, E ) Abstract : 1-((1 S, 2 R, 4 S, E )-3-Ferrocenylmethylidene-2-hydroxy-7, 7-dimethyl-2-(5-(trimethylsilyl)thiophen-2-yl)bicyclo[2.2.1]heptan-1-yl)- N, N -dimethylmethanesulfonamide: C30 H41 FeNO3 S2 Si [ α ]D 20 = −210.2 ( c 1.00, CHCl3 ) Source of chirality: (1 S )-(+)-camphor-10-sulfonyl chloride Absolute configuration: (1 S, 2 R, 4 S, E ) Abstract : 1-((1 S, 2 R, 4 S, E )-2-(Benzo[ d ]thiazol-2-yl)-3-ferrocenylmethylidene-2-hydroxy-7, 7-dimethylbicyclo[2.2.1]heptan-1-yl)- N, N -dimethylmethanesulfonamide: C30 H34 FeN2 O3 S2 [ α ]D 20 = −208.9 ( c 0.34, CHCl3 ) Source of chirality: (1 S )-(+)-camphor-10-sulfonyl chloride Absolute configuration: (1 S, 2 R, 4 S, E ) Abstract : 2-((1 R, 2 R, 4 S, E )-3-Ferrocenylmethylidene-2-hydroxy-1, 7, 7-trimethylbicyclo[2.2.1]heptan-2-yl)acetonitrile: C23 H27 FeNO [ α ]D 20 = −49.0 ( c 0.74, CHCl3 ) Source of chirality: (1 R )-(+)-camphor Absolute configuration: (1 R, 2 R, 4 S, E ) Abstract : 1-((1 S, 2 R, 4 S, E )-2-(Cyanomethyl)-3-ferrocenylmethylidene-2-hydroxy-7, 7-dimethylbicyclo[2.2.1]heptan-1-yl)- N, N -dimethylmethanesulfonamide: C25 H32 FeN2 O3 S [ α ]D 20 = −98.7 ( c 0.54, CHCl3 ) Source of chirality: (1 S )-(+)-camphor-10-sulfonyl chloride Absolute configuration: (1 S, 2 R, 4 S, E ) Abstract : (1 R, 2 R, 4 S, E )-2-(2-Aminoethyl)-3-ferrocenylmethylidene-1, 7, 7-trimethylbicyclo[2.2.1]heptan-2-ol: C23 H31 FeNO [ α ]D 20 = −20.5 ( c 0.44, CHCl3 ) Source of chirality: (1 R )-(+)-camphor Absolute configuration: (1 R, 2 R, 4 S, E ) Abstract : 1-((1 S, 2 R, 4 S, E )-2-(2-Aminoethyl)-3-ferrocenylmethylidene-2-hydroxy-7, 7-dimethylbicyclo[2.2.1]heptan-1-yl)- N, N -dimethylmethanesulfonamide: C25 H36 FeN2 O3 S [ α ]D 20 = −28.2 ( c 0.54, CHCl3 ) Source of chirality: (1 S )-(+)-camphor-10-sulfonyl chloride Absolute configuration: (1 S, 2 R, 4 S, E ) Abstract : (1 R, 2 R, 4 S, E )-3-Ferrocenylmethylidene-2-(2-(isoindolin-2-yl)ethyl)-1, 7, 7-trimethylbicyclo[2.2.1]: C31 H37 FeNO [ α ]D 20 = +51.3 ( c 0.39, CHCl3 ) Source of chirality: (1 R )-(+)-camphor Absolute configuration: (1 R, 2 R, 4 S, E ) Abstract : 1-((1 S, 2 R, 4 S, E )-3-Ferrocenylmethylidene-2-hydroxy-2-(2-(isoindolin-2-yl)ethyl)-7, 7-dimethylbicyclo[2.2.1]heptan-1-yl)- N, N -dimethylmethanesulfonamide: C33 H42 FeN2 O3 S [ α ]D 20 = +16.7 ( c 0.18, CHCl3 ) Source of chirality: (1 S )-(+)-camphor-10-sulfonyl chloride Absolute configuration: (1 S, 2 R, 4 S, E )