Diversification of the Avarane Skeleton Toward Spiroetherone A
Abstract
Studies toward spiroetherone A uncovered an unexpectedly rich reactivity landscape within the avarane skeleton. An intramolecular Michael addition onto a quinone enabled access to the characteristic spiroenedione core of the natural product. Alongside this transformation, diverse and unanticipated reaction pathways emerged, generating structurally complex molecular architectures. These included an unusual S N Ar on an electron-rich arene, a McMurry-type ketone-ester coupling with concomitant reductive deoxygenation, or Wagner-Meerwein rearrangements furnishing oxaspiro[4.5]dienone and dihydrochromane scaffolds. As other divergent transformations developed, a (3 + 2) quinone monoacetal dimerization produced a dibenzofuran motif close to popolohuanone E, whereas a PIDA-mediated alkene-phenol nitrile cyclization/Ritter reaction sequence delivered an unprecedented pentacyclic bridged imidate. This work demonstrates how synthetic exploration toward complex natural products can reveal unforeseen modes of reactivity and skeletal diversification.
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BibTeX
@article{schoenn2026diversification,
title = {{Diversification of the Avarane Skeleton Toward Spiroetherone A}},
author = {Guillaume Schoenn and Régis Guillot and Cyrille Kouklovsky and Guillaume Vincent},
journal = {ChemistryEurope},
year = {2026},
month = aug,
doi = {10.1002/ceur.70350},
url = {https://hal.science/hal-05770600v1},
note = {CC BY-NC-SA 4.0},
}
RIS
TY - JOUR
TI - Diversification of the Avarane Skeleton Toward Spiroetherone A
AU - Guillaume Schoenn
AU - Régis Guillot
AU - Cyrille Kouklovsky
AU - Guillaume Vincent
PY - 2026
DA - 2026/08/27
JO - ChemistryEurope
DO - 10.1002/ceur.70350
UR - https://hal.science/hal-05770600v1
AB - Studies toward spiroetherone A uncovered an unexpectedly rich reactivity landscape within the avarane skeleton. An intramolecular Michael addition onto a quinone enabled access to the characteristic spiroenedione core of the natural product. Alongside this transformation, diverse and unanticipated reaction pathways emerged, generating structurally complex molecular architectures. These included an unusual S N Ar on an electron-rich arene, a McMurry-type ketone-ester coupling with concomitant reductive deoxygenation, or Wagner-Meerwein rearrangements furnishing oxaspiro[4.5]dienone and dihydrochromane scaffolds. As other divergent transformations developed, a (3 + 2) quinone monoacetal dimerization produced a dibenzofuran motif close to popolohuanone E, whereas a PIDA-mediated alkene-phenol nitrile cyclization/Ritter reaction sequence delivered an unprecedented pentacyclic bridged imidate. This work demonstrates how synthetic exploration toward complex natural products can reveal unforeseen modes of reactivity and skeletal diversification.
SN - 2751-4765
ER -