Ring-expansion reactions of Cyrene and derivatives with ethyl diazoacetate
Date
2025
Authors
Puschnig, J.
Lamb, O.
Sumby, C.J.
Greatrex, B.W.
Editors
Polyzos, A.
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Journal article
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Australian Journal of Chemistry, 2025; 78(5):CH24163-1-CH24163-5
Statement of Responsibility
Johannes Puschnig, Oscar Lamb, Christopher J. Sumby, Ben W. Greatrex
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Abstract
The ring expansion and homologation of the biomass derivative Cyrene (6,8-dioxabicyclo[3.2.1]octan-4-one) has been developed by Lewis-acid promoted reactions with ethyl diazoacetate. Insertion into the C3–C4 bond gave a ring-expanded β-ketoester regioisomer as an equilibrating mixture of diastereomers, which was subjected to a one-pot hydrolysis and decarboxylation to give the 7,9-dioxabicyclo[4.2.1]nonan-5-one system (homocyrene). The reactivity of homocyrene was then investigated in a series of transformations known for the parent 6,8-dioxabicyclo[3.2.1]octan-4-one system, including the Baeyer–Villiger oxidation affording S-6-(hydroxymethyl)pyran-2-one, which has been used for the synthesis of jasmine lactone, and another one-carbon ring expansion. The ring-expansion process for Cyrene could be used to prepare chiral C₆ and C₇ synthons on scale from biomass.
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© 2025 The Author(s) (or their employer(s)). Published by CSIRO Publishing. This is an open access article distributed under the Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC)