Enynones in Organic Synthesis. 6. Synthesis of Spirocyclic Methylenecyclopentenones and Analogs of the Methylenomycin Class of Antibiotics. Mechanism of Phenol …

PA Jacobi, LM Armacost, HL Brielmann…

Index: Jacobi; Armacost; Brielmann; Cann; Kravitz; Martinelli Journal of Organic Chemistry, 1994 ,  vol. 59,  # 18  p. 5292 - 5304

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Citation Number: 12

Abstract

Spirocyclic methylenecyclopentenones of general structure 18 were prepared in a single step from bis-acetylenic alcohols 29 by a process involving initial oxy-Cope rearrangement to afford (2)-enynones 30-Z followed by electrocyclic ring closure. Mechanistic studies indicate that the initial step leading from 30-2 to 18 is a thermal l, &prototropic shiR to afford dienols which can cyclize by a symmetry-allowed (jt4s+ u2s+ 9,) process. This last step is ...