Synthesis of protected, chiral α,α-disubstituted α-amino acids via a Beckmann rearrangement

Tetrahedron Letters

Volumn 39, Issue 17, 1998, Pages 2475-2478

  Frutos, Rogelio P ^a   Spero, Denice M ^a  

^a BOEHRINGER INGELHEIM PHARMACEUTICALS INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALPHA AMINO ACID; OXIME DERIVATIVE;

AMINO ACID ANALYSIS; ARTICLE; CHIRALITY; ENANTIOMER; GENE REARRANGEMENT; RACEMIC MIXTURE; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

EID: 0032560044     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)00309-8     Document Type: Article

References (25)

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9. 9. For the synthesis of chiral α,α-disubstituted α-amino acids via enzymatic resolutions see: a) Parmar, V. S., Singh, A., Bisht, K. S., Kumar, N., Belokon, Y. N., Kocketkov, K. A., Ikonnikiv, N. S., Orlova, S. A., Taranov, V. I., Saveleva, T. F. J. Org. Chem. 1996, 61, 1223 and references cited therein.
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18. b) The optical purity of the resulting β-ketoesters was determined by chiral HPLC (Chiralpak AS column, hexanes/ethanol, 100:0.5 v/v, 1.5 mL/min).
19. 3) δ 23.0, 23.7, 40.9, 52.4, 60.8, 126.7, 128.0, 129.7, 16.3, 169.5, 174.2.
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24. 22. The distribution of products correlates with the ability of the ester R group to stabilize a positive charge. Therefore the mechanism probably involves nucleophilic attack of the ester carbonyl oxygen into the oxime nitrogen.
25. 23. The optical purity of the products was determined by chiral HPLC (Chiralpak AD column, hexane/ethyl acetate/diethyl amine, 85:15:0.5 v/v, 1 mL/min), and was found to be consistent with the optical purity of the starting β-ketoesters.