Highly selective R,S-coordination of non racemic (1R,2R)-(1,2-dialkyl)-1,2- diamine cyclohexane derivatives to palladium dichloride

Chemical Communications

Volumn , Issue 6, 2007, Pages 583-585

  Rafii, Esfandiar ^a   Dassonneville, Benjamin ^a   Heumann, Andreas ^a  

^a AIX MARSEILLE UNIVERSITY   (France)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOHEXANE DERIVATIVE; LIGAND; PALLADIUM COMPLEX;

ARTICLE; ASYMMETRIC SYNTHESIS; COMPLEX FORMATION; ENANTIOSELECTIVITY; REACTION ANALYSIS; STEREOCHEMISTRY; STEREOSPECIFICITY;

EID: 33846842093     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/b613961b     Document Type: Article

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23. See electronic supplementary material for the complete NMR data
24. The presence of fluorine as a spectator atom in the ligand is a valuable aid in the NMR detection of the composition of the complex structure and the reaction mixtures
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28. 19F NMR δ: -111.2 (21%, dl-1), -111.7 and -112.0 (55%, R,S), -111.8 (20%, dl-2), -114.5 (3%, unknown). The predominance of the R,S isomer is recognized by the presence of the two fluorine resonances with a ratio of 1: 1. The analysis of the proton spectra of the mixture is also diagnostic. Theoretically we are expecting eight doublets for the benzylic protons. In reality we visualize (and attribute) seven doublets: dl-1 (1R,2R)-5 δ: 4.47, 3.26; dl-2 (1R,2R)-5: 4.96, 2.96 (partially hidden); R,S (1R,2R)-5c: 4.23, 3.54, and 4.74, 3.67. It was possible to obtain mixtures with variable dl and R,S proportions via chromatography on silica (eluent: dichloromethane-methanol 95: 5)
29. 2, 25°C, 1 h
30. Complex 6b is insoluble in most common solvents and we could only obtain the proton and fluorine NMR spectra in D6-DMSO. Except for the visibility of the presence of two compounds, confirmed by proton resonances, too, we are unable for the moment to analyze completely the NMR data
31. 2 with the same R,S structure comparable to R,S-(1R,2R)-3 according to the NMR spectra
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