American Chemical Society
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Functionalized Tetrahydrofurans from Alkenols and Olefins/Alkynes via Aerobic Oxidation−Radical Addition Cascades

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journal contribution
posted on 2011-03-23, 00:00 authored by Patrick Fries, Daniel Halter, Alexander Kleinschek, Jens Hartung
Aerobic oxidation of alkyl- and phenyl-substituted 4-pentenols (bishomoallyl alcohols), catalyzed by cobalt(II) complexes in solutions of γ-terpinene or cyclohexa-1,4-diene, stereoselectively gave tetrahydrofurylmethyl radicals. Cyclized radicals were trapped with monosubstituted olefins (e.g., acrylonitrile, methyl acrylate), (E)- and (Z)-1,2-diacceptor-substituted olefins (e.g., dimethyl fumarate, fumarodinitrile, N-phenyl maleic imide), and ester-substituted alkynes (e.g., ethyl propynoate). Oxidation−addition cascades thus furnished side-chain-substituted (CN, CO2R, COR, or SO2R) di- and trisubstituted tetrahydrofurans in stereoselective reactions (2,3-trans, 2,4-cis, and 2,5-trans). A diastereomerically pure bistetrahydrofuran was prepared in a cascade consisting of two aerobic oxidations, one alkyne addition, and one final H-atom transfer.