Nils Frank, Moreshwar B. Chaudhari, Markus Leutzsch, Benjamin Helmich‐Paris, Paolo Cleto Bruzzese, Darryl F. Nater, Nils Nöthling, Alexander Schnegg, Siegfried R. Waldvogel, Benjamin List
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.