MTPA vs MPA in the determination of the absolute configuration of chiral alcohols by 1H NMR

Journal of Organic Chemistry

Volumn 61, Issue 24, 1996, Pages 8569-8577

  Latypov, Sh K ^a,b   Seco, J M ^a   Quinoa E ^a   Riguera, R ^a  

^a UNIVERSITY OF SANTIAGO DE COMPOSTELA   (Spain)

^b A E ARBUZOV INSTITUTE OF ORGANIC AND PHYSICAL CHEMISTRY   (Russian Federation)

Author keywords

[No Author keywords available]

Indexed keywords

2 BUTANOL; ALKANOL; BORNEOL; ISOPULEGOL; UNCLASSIFIED DRUG;

ARTICLE; DERIVATIZATION; DRUG STRUCTURE; ENANTIOMER; NUCLEAR MAGNETIC RESONANCE; TECHNIQUE; THEORY;

EID: 0029913951     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960719i     Document Type: Article

References (33)

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6. RS is the difference between the chemical shift in the (R)-derivative minus that of the same proton in the (S)-derivative.
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26. For simplification purposes and in coherence with previous papers (see ref 5), we will refer to these compounds by (R/S)-n, where (R/S) indicates the configuration at the chiral center of the auxiliary reagent (MPA or MTPA) and n is the digit that identifies the parent alcohol.
27. The H(6′e) in (R)-4 and (S)-6, H(6′a) in (S)-7, and H(3′) in (R)-8 are affected by the anisotropic effect of the carbonyl, and its interference explains the high-field shift observed at lower anisotropic effect of the carbonyl, and its interference explains the high-field shift observed at lower temperature.
28. 2 - 4/1, T = 153 K): δ(8′) = 0.895 ppm, δ(9′) = 0.681 ppm.
29. 2 - 4/1, T = 298 K): δ(10′) = 0.88 ppm.
30. Protons H(6′) in (R)-10, H(5′) and H(6′) in (R)-9, H(1′) in (R)-11, H(2′), H(8′), and H(9′) in (S)-10, H(8′), H(9′), and H(10′) in (S)-9, and H(3′) and H(4′) in (S)-11 are unaffected by the shielding cone of the phenyl ring, and their chemical shifts are taken as reference for comparison with MTPA esters.
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