Ring-expansion reactions of Cyrene and derivatives with ethyl diazoacetate
| dc.contributor.author | Puschnig, J. | |
| dc.contributor.author | Lamb, O. | |
| dc.contributor.author | Sumby, C.J. | |
| dc.contributor.author | Greatrex, B.W. | |
| dc.contributor.editor | Polyzos, A. | |
| dc.date.issued | 2025 | |
| dc.description.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. | |
| dc.description.statementofresponsibility | Johannes Puschnig, Oscar Lamb, Christopher J. Sumby, Ben W. Greatrex | |
| dc.identifier.citation | Australian Journal of Chemistry, 2025; 78(5):CH24163-1-CH24163-5 | |
| dc.identifier.doi | 10.1071/CH24163 | |
| dc.identifier.issn | 0004-9425 | |
| dc.identifier.issn | 1445-0038 | |
| dc.identifier.orcid | Sumby, C.J. [0000-0002-9713-9599] | |
| dc.identifier.uri | https://hdl.handle.net/2440/147324 | |
| dc.language.iso | en | |
| dc.publisher | CSIRO Publishing | |
| dc.relation.grant | http://purl.org/au-research/grants/arc/LE210100163 | |
| dc.rights | © 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) | |
| dc.source.uri | https://doi.org/10.1071/ch24163 | |
| dc.subject | carbene; cyrene; diazo compounds; Jasmine lactone; levoglucosenone; organic green chemistry; ring expansion; valerolactone | |
| dc.title | Ring-expansion reactions of Cyrene and derivatives with ethyl diazoacetate | |
| dc.type | Journal article | |
| pubs.publication-status | Published |