Visible light-driven conjunctive olefination Dario Filippini and Mattia Silvi University of Nottingham, UK
Late-stage functionalization is a convenient strategy in organic synthesis with applications in relevant fields of science and technology, including drug discovery.[1] In this report,[2] we disclose a metal-free cross-coupling process which allows practical connection of complex molecular fragments bearing carboxylic acids and aldehydes, ubiquitous functional groups in chemistry. The reaction merges two cornerstones of organic synthesis—namely, the Wittig reaction[3] and photoredox catalysis[4]—in a catalytic cycle that couples a radical addition process with the redox generation of a phosphonium ylide. The procedure is highly functional group tolerant and can be used for the late-stage functionalization of native-form natural products and bioactive molecules without the need of exogeneous functional groups and no (or very limited) use of protecting groups. The chemistry connects the fragments forging a new alkene functional group with a programmable E–Z stereochemistry.
References 1. B rgel, J., Ritter, T., Late-Stage Functionalization. Chem ., 6 , 1877-1887 (2020). 2. Filippini, D., Silvi, M. Visible light-driven conjunctive olefination. Nat. Chem . 14 ,66–70 (2022).
3. Wittig, G. Nobel Lecture: from Diyls to My Idyll https://www.nobelprize.org/ uploads/2018/06/wittig-lecture.pdf (1979).Prier, C. K., Rankic, D. A. & MacMillan, D. W. C. Visible light photoredox catalysis with transition metal complexes: applications in or anic synthesis. Chem. Rev . 113 , 5322–5363 (2013).
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