Issue 39, 2014

A unifying mechanism for the rearrangement of vinyl allene oxide geometric isomers to cyclopentenones

Abstract

A new mechanism for the rearrangement of vinyl allene oxide geometric isomers to stereodefined cyclopentenones is proposed based on DFT computations. This mechanism comprises two steps, first the ring opening of the oxirane to give a vinylcyclopropanone, and then a [1,3]-C sigmatropic rearrangement. Depending primarily on the allene oxide double bond geometry the stepwise pathway is either competitive (for E allene oxides) or favored (for Z allene oxides) relative to the already described SN2-like concerted pathway. All bond-forming reactions take place through helically chiral transition states, which allows the stereochemical information of the substrates to be transferred to that of the products, in particular in the case of (enantiopure) Z allene oxides. In addition to revealing one more of the fascinating mechanisms with memory of chirality, the results deepen our understanding of the important jasmonate and clavulone biosynthetic pathways that occur in plants and corals.

Graphical abstract: A unifying mechanism for the rearrangement of vinyl allene oxide geometric isomers to cyclopentenones

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
13 Mar 2014
Accepted
03 Jun 2014
First published
03 Jun 2014

Org. Biomol. Chem., 2014,12, 7694-7701

Author version available

A unifying mechanism for the rearrangement of vinyl allene oxide geometric isomers to cyclopentenones

A. B. González-Pérez, A. Grechkin and Á. R. de Lera, Org. Biomol. Chem., 2014, 12, 7694 DOI: 10.1039/C4OB00562G

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