Synthesis of highly substituted 3-formylfurans by a gold(I)-catalyzed oxidation/1,2-alkynyl migration/cyclization cascade

• Verfasst von: Wang, Tao [VerfasserIn]
• Verfasst von: Shi, Shuai [VerfasserIn]
• Verfasst von: Hansmann, Max M. [VerfasserIn]
• Verfasst von: Rettenmeier, Eva [VerfasserIn]
• Verfasst von: Rudolph, Matthias [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Titel: Synthesis of highly substituted 3-formylfurans by a gold(I)-catalyzed oxidation/1,2-alkynyl migration/cyclization cascade
• Verf.angabe: Tao Wang, Shuai Shi, Max M. Hansmann, Eva Rettenmeier, Matthias Rudolph, and A. Stephen K. Hashmi
• E-Jahr: 2014
• Jahr: February 24, 2014
• Umfang: 5 S.
• Fussnoten: Gesehen am 29.07.2020
• Titel Quelle: Enthalten in: Angewandte Chemie / International edition
• Ort Quelle: Weinheim : Wiley-VCH, 1962
• Jahr Quelle: 2014
• Band/Heft Quelle: 53(2014), 14, Seite 3715-3719
• ISSN Quelle: 1521-3773
• DOI: doi:10.1002/anie.201310146
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: alkynyl migration
• Sach-SW: cyclization
• Sach-SW: furans
• Sach-SW: gold
• Sach-SW: N-oxides
• K10plus-PPN: 1725865068

Abstract

3-Formylfuran derivatives are core structures of a variety of bioactive natural products. However, procedures for their preparation are still rare and generally inefficient in terms of atom economy: These methods require multiple steps or harsh reaction conditions and show selectivity problems. An efficient gold(I)-catalyzed cascade reaction that leads to 3-formylfurans from easily accessible starting materials is now described. A wide variety of 3-formylfurans were obtained from the corresponding symmetric and unsymmetric 1,4-diyn-3-ols in the presence of an N-oxide in good to excellent yields. Isotope-labeling experiments as well as DFT calculations support a mechanism in which, after an initial oxygen transfer, a 1,2-alkynyl migration is favored over a hydride shift; a cyclization ensues to afford the desired functionalized furan core.