Resolution of pentafluorophenyl esters using oxazolidin-2-ones

Tetrahedron Letters

Volumn 51, Issue 45, 2010, Pages 5892-5895

  Al Shaye, Najla ^a   Eames, Jason ^a  

^a UNIVERSITY OF HULL   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

FLUORINE DERIVATIVE; OXAZOLIDINONE DERIVATIVE; PHENYL GROUP;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; DIASTEREOISOMER; QUANTUM YIELD; REACTION ANALYSIS; SYNTHESIS;

EID: 77957800150     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2010.08.109     Document Type: Article

References (31)

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19. 1H NMR (400 MHz) spectroscopy]. For oxazolidin-2-one (S,S)-anti-3, the PhCHN double doublet is at 5.32 ppm (1H, dd, J = 8.8 and 3.2). Whereas, for oxazolidin-2-one (R,S)-syn-3, the PhCHN double doublet is 5.45 ppm (1H, dd, J = 9.0 and 5.1).
20. The enantiomeric excess was determined through hydrolysis of the active ester to give the corresponding carboxylic acid. The enantiomeric excess of this carboxylic acid was determined through statistical anhydride formation by treatment with DCC. For further information, see: E. Coulbeck, and J. Eames Tetrahedron: Asymmetry 20 2009 635
21. After 1 min - the active ester (S)-2 was recovered in 30% yield with 90% ee. The enantiomeric excess was confirmed by specific rotation and self-coupling; see Ref. 6.
22. For 1 equiv - the active ester (S)-2 was recovered in 35% yield with 44% ee. The enantiomeric excess was confirmed by specific rotation and self-coupling; see Ref. 6.
23. The following enantiomerically enriched active esters were isolated; Scheme 4, entry 1 - (S)-2; 35%; 46% ee; entry 2 - (S)-4; 43%; 80% ee; entry 3 - (rac)-6; 90%; entry 4 - (S)-8; 42%; 55% ee; entry 5 - (S)-10; 42%; 74% ee; entry 6 - (S)-12; 20%; 65% ee; entry 7 - (S)-14; 37%; 63% ee.
24. The% ee of the recovered active esters were comparable (within experimental error) to the theoretical value based on the %yield (±10%) and %de of the oxazolidin-2-one adduct.
25. Addition of the lithiated oxazolidin-2-one (S)-1 to the active ester (rac)-12 is stereospecific as addition to the enantiomerically pure active ester (R)-12 gave exclusively the major diastereoisomeric oxazolidin-2-one (R,S)-syn-13 in 54% yield with >98% de.
26. The enantiomerically enriched active ester 2 was isolated; Scheme 5, entry 1 - 35%; (S)-54% ee; entry 2 - 14%; (S)-23% ee; entry 3 - 59%; (S)-17% ee; entry 4 - 32%; (S)-53% ee; entry 5 - 24%; (R)-56% ee; entry 6 - 15%; (R)-54% ee; entry 7 - 37%; (R)-66% ee; entry 8 - 17%; (R)-64% ee.
27. The enantiomerically enriched active ester 2 was isolated; Scheme 6, entry 1 - 25%; (R)-32% ee; entry 2 - 17%; (R)-68% ee; entry 3 - 32%; (R)-37% ee; entry 4 - 15%; (R)-19% ee; entry 5 - 14%; (S)-44% ee; 4%; (S)-4% ee; entry 8 - 31%; (R)-36% ee; entry 9 - 37%; (S)-36% ee; entry 10 - 9%; (S)-16% ee; entry 12 - 19%; (R)-33% ee; entry 14 - 50%; 6% ee.
28. The stereochemistry of the Seebach adducts, (R,S)-syn-17, (S,S)-anti-29 and (S,S)-anti-33, were confirmed by stereospecific synthesis.
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