Diastereoselective synthesis of 6-functionalized 4-aryl-1,3-oxazinan-2-ones and their application in the synthesis of 3-aryl-1,3-aminoalcohols and 6-arylpiperidine-2,4-diones


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Mangelinckx S., Nural Y., DÖNDAŞ H. A. , Denolf B., Sillanpaa R., De Kimpe N.

TETRAHEDRON, vol.66, no.23, pp.4115-4124, 2010 (Peer-Reviewed Journal) identifier identifier

  • Publication Type: Article / Article
  • Volume: 66 Issue: 23
  • Publication Date: 2010
  • Doi Number: 10.1016/j.tet.2010.03.113
  • Journal Name: TETRAHEDRON
  • Journal Indexes: Science Citation Index Expanded, Scopus
  • Page Numbers: pp.4115-4124
  • Keywords: Cyclocarbamation, 1,3-Oxazinan-2-ones, 1,3-Aminoalcohols, Piperidine-2,4-diones, ASYMMETRIC TOTAL-SYNTHESIS, CHIRAL BUILDING-BLOCK, STEREOSELECTIVE-SYNTHESIS, ALPHA-AMINO, INTRAMOLECULAR AMIDOALKYLATION, STREPTOMYCES-CLAVULIGERUS, CONCISE SYNTHESIS, SPERABILLINS-B, ACID, ROUTE

Abstract

Halocyclocarbamation of benzyl N-(1-phenyl-3-butenyl)carbamates afforded 6-functionalized 4-aryl-1,3-oxazinan-2-ones with moderate to excellent diastereoselectivity depending on the N-substituent. Importantly, in contrast to reported cyclocarbamations of homoallylic carbamates, which are generally trans-diastereoselective, cyclization of N-unsubstituted Cbz-protected homoallylamines led to cis-1,3-oxazinan-2-ones, predominantly. The use of N-benzylated and in situ prepared N-silylated derivatives resulted however in trans-selectivity. Transition states are proposed to explain the stereochemical influence of the N-substituent on the cyclocarbamations. The functionalized 1,3-oxazinan-2-ones could be further elaborated towards biologically or synthetically important 6-arylpiperidine-2,4-diones and 3-aryl-1,3-aminoalcohols. (C) 2010 Elsevier Ltd. All rights reserved.