Synthesis of (−)-Morphine

Douglass F. Taber,* Timothy D. Neubert, and Arnold L. Rheingold§
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716
J. Am. Chem. Soc., 2002, 124 (42), pp 12416–12417
DOI: 10.1021/ja027882h
Publication Date (Web): September 28, 2002
Copyright © 2002 American Chemical Society
*

 To whom correspondence should be addressed. E-mail:  taberdf@udel.edu.

,
§

 For X-ray analysis.

Abstract

Abstract Image

The preparation of the diastereomerically pure β-tetralone ketal 4 is reported. Intramolecular alkylidene C−H insertion followed by hydrolysis of 4 proceeded to give the enantiomerically pure cyclopentene 15. The key step in this synthesis was the bis-intramolecular cyclization of keto aldehyde 2 to give the tetracyclic intermediate 20. Enone 20 was converted over several steps to (−)-morphine 1.

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History

  • Published In Issue October 23, 2002
  • Received July 26, 2002

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