Diastereoselective Electrophilic Amination of Chiral 1-Benzoyl-2,3,5,6-tetrahydro-3-methyl-2-(1-methylethyl)pyrimidin-4(1H)-one for the Asymmetric Syntheses of α-Substituted α,β-Diaminopropanoic Acids

✍ Scribed by Elena Castellanos; Gloria Reyes-Rangel; Eusebio Juaristi

• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: German
• Weight: 160 KB
• Volume: 87
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.200490073

✦ Synopsis

Abstract

The chiral compounds (R)‐ and (S)‐1‐benzoyl‐2,3,5,6‐tetrahydro‐3‐methyl‐2‐(1‐methylethyl)pyrimidin‐4(1__H__)‐one ((R)‐ and (S)‐1), derived from (R)‐ and (S)‐asparagine, respectively, were used as convenient starting materials for the preparation of the enantiomerically pure α‐alkylated (alkyl=Me, Et, Bn) α,β‐diamino acids (R)‐ and (S)‐11–13. The chiral lithium enolates of (R)‐ and (S)‐1 were first alkylated, and the resulting diasteroisomeric products 5–7 were aminated with ‘di(tert‐butyl) azodicarboxylate’ (DBAD), giving rise to the diastereoisomerically pure (≥98%) compounds 8–10. The target compounds (R)‐ and (S)‐11–13 could then be obtained in good yields and high purities by a hydrolysis/hydrogenolysis/hydrolysis sequence.