The photohydrolysis of furans

• 成果类型: Article
• 署名作者: Frank, Nils; Chaudhari, Moreshwar B.; Leutzsch, Markus; Helmich-Paris, Benjamin; Bruzzese, Paolo Cleto; Nater, Darryl; Nothling, Nils; Schnegg, Alexander; Waldvogel, Siegfried R.; List, Benjamin
• 署名单位: Max Planck Society
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-8075; 1095-9203
• DOI: 10.1126/science.aec6532
• 发表日期: 2026-01-15
• 页码: 267-274
• 关键词: STEREOSPECIFIC TOTAL-SYNTHESIS; ZETA-VALENCE QUALITY; PHOTOCHEMICAL ISOMERIZATION; EPIPENTENOMYCIN-I; facile synthesis; basis-sets; ketones; efficient; ECONOMY; suppression

摘要

The defossilization of the chemical industry is accelerated by the shift from petroleum- to biomass-based feedstocks. At the center stage are bioderived furans, from which valuable platform chemicals can be obtained exclusively through oxidative or reductive processes. By contrast, the conceptually straightforward redox-neutral hydrolysis of furan to succinaldehyde and 2-substituted furans to 1,4-ketoaldehydes has been considered unfeasible owing to their endergonicity and polymerization side reactivity. In this work, we report the realization of this uphill furan hydrolysis through photocatalysis involving a highly strained, 10-membered 1,6-dioxecine intermediate. Succinaldehyde, as well as 1,4-ketoaldehydes, can be directly obtained from furans. Additionally, furfural derivatives undergo redox-enhanced Piancatelli rearrangements, accessing antimicrobial natural products (+/-)-Terrein and (+/-)-epi-Pentenomycins. The methodology was applied to the redox-neutral production of common industrial fine chemicals, avoiding wasteful redox detours typical in biomass-based synthesis.