Pseudoephedrine as a practical chiral auxiliary for the synthesis of highly enantiomerically enriched carboxylic acids, alcohols, aldehydes, and ketones

Journal of the American Chemical Society

Volumn 119, Issue 28, 1997, Pages 6496-6511

  Myers, Andrew G ^a   Yang, Bryant H ^a   Chen, Hou ^a   McKinstry, Lydia ^a   Kopecky, David J ^a   Gleason, James L ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; ALKANOL; AMIDE; CARBOXYLIC ACID DERIVATIVE; KETONE; PSEUDOEPHEDRINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; ENANTIOMER; IN VITRO STUDY; INFRARED SPECTROPHOTOMETRY; MASS SPECTROMETRY; METHODOLOGY; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030810476     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970402f     Document Type: Article

References (79)

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37. In these and all subsequent alkylation reactions, care was taken to avoid adventitious diastereomeric enrichment upon purification and de values reported reflect those of the crude reaction mixtures.
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75. In each case, an authentic sample of the minor diastereomeric alkylation product was prepared for comparative analysis (chiral capillary GC analysis of the corresponding trimethylsilyl ether or acetate ester). In the case of amides 16, 21, 26, 27, and 29-31, diastereomeric mixtures of α-epimers were obtained by epimerization with LDA (5 equiv) or lithium 2,2,6,6-tetramethylpiperidide (5 equiv) in THF for 5 h at 23 °C followed by quenching with aqueous ammonium chloride solution. Amide 28 was epimerized by stirring with lithium chloride (5 equiv) in N,N-dimethylformamide at 23 °C for 12 h. Each of the remaining alkylation products in Tables 2 and 3 was epimerized by stirring the substrate with trifluoroacetic acid (10 equiv) in THF at reflux for 1 h (effecting N → O acyl transfer as well as α-epimerization), followed by neutralization with aqueous sodium bicarbonate solution at 23 °C for 24 h (causing O → N acyl transfer).
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