What question did this study set out to answer?

This research aims to facilitate the synthesis of complex bicyclic structures from 2-oxabicyclo[3.3.0]octenes.

July 15, 2026

Skeletal Metamorphosis of 2-Oxabicyclo3.3.0octenes into Bridged Bicyclo3.2.1octenes: A Strategy for Complex Architecture Synthesis

SSShumpei ShimojiHokkaido University of Education RHR HibinoHokkaido University of Education TSTsukasa ShimakawaUniversity of Illinois Urbana-Champaign

Key Points

This research aims to facilitate the synthesis of complex bicyclic structures from 2-oxabicyclo[3.3.0]octenes.
Yb(OTf)3-catalyzed transformation of 2-oxabicyclo[3.3.0]octenes
Utilization of density functional theory for mechanistic insights
Demonstration of regio- and stereoselective construction of the grayanane ACD core.
Achieved good to excellent yields in the transformation
Proved the existence of chelation-stabilized intermediates through density functional theory
Established an effective strategy for late-stage skeletal editing in complex molecular synthesis.

Abstract

Highly functionalized bicyclo3.2.1octane/octene motifs are prevalent in bioactive natural products. We report Yb(OTf) 3 -catalyzed fused-to-bridged metamorphosis of 2-oxabicyclo3.3.0octenes into these bridged architectures in good to excellent yields. Experimental and density functional theory studies support a stepwise rearrangement pathway involving chelation-stabilized intermediates. The utility of this transformation was demonstrated by the regio- and stereoselective construction of the grayanane ACD tricyclic core with an exceptional tolerance for acid-labile groups. This late-stage skeletal editing strategy expands the retrosynthetic strategies for complex molecular synthesis.

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