Chiral thiols: The assignment of their absolute configuration by 1H NMR

Organic Letters

Volumn 9, Issue 24, 2007, Pages 5015-5018

  Porto, Silvia ^a   Seco, José Manuel ^a   Ortiz, Aurelio ^b   Quiñoá, Emilio ^a   Riguera, Ricardo ^a  

^a UNIVERSITY OF SANTIAGO DE COMPOSTELA   (Spain)

^b BENEMÉRITA UNIVERSIDAD AUTÓNOMA DE PUEBLA   (Mexico)

Author keywords

[No Author keywords available]

Indexed keywords

LIGAND; PROTON; THIOL DERIVATIVE;

ARTICLE; CHEMISTRY; CONFORMATION; METHODOLOGY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STANDARD; STEREOISOMERISM;

LIGANDS; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR CONFORMATION; PROTONS; REFERENCE STANDARDS; STEREOISOMERISM; SULFHYDRYL COMPOUNDS;

EID: 36849024432     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol7022196     Document Type: Article

References (17)

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7. Two previous reports dealing with the use of NMR for this purpose consisted of empirical methods using acetic acid derivatives tested with a small number of thiols (three and two, respectively). See: (a) Helmchen, G.; Schmierer, R. Angew. Chem., Int. Ed. Engl. 1976, 15, 703.
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9. RS for a given substituent is the difference between its chemical shift in the (R)-CDA derivative minus that in the (S)-CDA derivative.
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11. Conformational analysis on simple thioesters had previously shown that the cis planar form around the Φ3 angle was the prevailing conformation in a variety of solvents. See: (a) Nagy, P. I.; Tejada, F. R.; Sarver, J. G.; Messer, W. S., Jr. J. Phys. Chem. A 2004, 108, 10173.
12. (b) Deerfield, D. W., II; Pedersen, L. G. J. Mol. Struct. (THEOCHEM) 1995, 358, 99.
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14. In MPA amides, ap forms are the most populated and NMR relevant. In MPA esters, where the aplsp forms are also present, the equilibria are shifted in the opposite way and sp conformers are major and NMR relevant (Figure 4a).
15. García, R.; Seco, J. M.; Vázquez, S. A.; Quiñoá, E.; Riguera, R. J. Org. Chem. 2006, 71, 1119 and references therein.
16. Colorless prisms of the (S)-MPA thioester of 1 -thio-β-D-glucose tetraacetate (10) were recrystallized from diethyl ether/hexane. Crystallography data have been deposited with the Cambridge Crystallographic data center and allocated the deposition number CCDC 650882.
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