Thiophilic ring-opening and rearrangement reactions of epoxyketone natural products
Related Experiment Video
Updated: Oct 13, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Abstract:
Thiol additions to the highly functionalized core structures of aranorosin- and manumycin-type antibiotics reveal the general reactivity patterns of epoxyketone natural products. Rapid hemiacetal and hydrate formations decrease the reactivity of the epoxyketone moiety in aqueous media toward the cellular scavenger glutathione, and secondary 1,2-shift, elimination, aromatization and intramolecular aldol reactions provide novel reaction pathways. In a hydrophobic environment, the thiol-capture function of the ketone moiety facilitates electrophilic attack.
Related Concept Videos
Preparation of Epoxides
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Acid-Catalyzed Ring-Opening of Epoxides
Base-Catalyzed Ring-Opening of Epoxides
Thermal and Photochemical Electrocyclic Reactions: Overview
Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

