Rapid Assembly of Tetrasubstituted Furans via Pummerer-Type Rearrangement
Open Access
- 5 January 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 143 (2), 1216-1223
- https://doi.org/10.1021/jacs.0c12194
Abstract
Despite the many methods available for the synthesis of furans, few methods remain that allow for the custom-made assembly of fully substituted furans. Here we report a powerful protocol to rapidly construct tetrasubstituted, orthogonally functionalized furans under mild reaction conditions. The developed method involves the regioselective ring-opening of readily available 2,5-dihydrothiophenes followed by an oxidative cyclization to provide the heterocycle. The selective oxidation at sulfur is promoted by N-chlorosuccinimide as an inexpensive reagent and proceeds at ambient temperature in high yield within 30 min. The obtained furans serve as exceptionally versatile intermediates and were shown to participate in a series of valuable postmodifications. The fate of the initial sulfonium intermediate was investigated by mechanistic experiments, and computational studies revealed the existence of an unprecedented Pummerer-type rearrangement. The potential for organic synthesis is highlighted by the total synthesis of bisabolene sesquiterpenoids (pleurotins A, B, and D).Funding Information
- Austrian Science Fund FWF (M2005, P31023-NBL)
- Tyrolean Science Fund TWF (F.16642/5-2019, UNI-0404/2340)
This publication has 39 references indexed in Scilit:
- Yne–Enones Enable Diversity-Oriented Catalytic Cascade Reactions: A Rapid Assembly of ComplexityAccounts of Chemical Research, 2020
- Modular Synthesis of Furans with up to Four Different Substituents by a trans‐Carboboration StrategyAngewandte Chemie, 2020
- Synthetic Entry to Polyfunctionalized Molecules through the [3+2]-Cycloaddition of Thiocarbonyl YlidesJournal of the American Chemical Society, 2019
- Furan Oxidation Reactions in the Total Synthesis of Natural ProductsSynthesis, 2018
- Furans as Versatile Synthons: Total Syntheses of Caribenol A and Caribenol BJournal of the American Chemical Society, 2017
- The Modern Face of Synthetic Heterocyclic ChemistryThe Journal of Organic Chemistry, 2016
- Modern advances in heterocyclic chemistry in drug discoveryOrganic & Biomolecular Chemistry, 2016
- Sesquiterpenoids with PTP1B Inhibitory Activity and Cytotoxicity from the Edible Mushroom Pleurotus citrinopileatusPlanta Medica, 2016
- Total Synthesis of the Leucosceptroid Family of Natural ProductsJournal of the American Chemical Society, 2015
- Transition Metal-Mediated Synthesis of Monocyclic Aromatic HeterocyclesChemical Reviews, 2013