TY - JOUR
T1 - Taking electrodecarboxylative etherification beyond Hofer–Moest using a radical C–O coupling strategy
AU - Martínez, Ángel Manu
AU - Hayrapetyan, Davit
AU - van Lingen, Tim
AU - Dyga, Marco
AU - Gooßen, Lukas J.
N1 - Funding Information:
Funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy—EXC 2033—390677874—RESOLV, FOR 2982/1 —UNODE, and GO863/12-1, BMBF and the state of NRW (Center of Solvation Science “ZEMOS”). We thank Prof. N. Plumeré and Dr H. Li for advice and support.
Publisher Copyright:
© 2020, The Author(s).
PY - 2020/12/1
Y1 - 2020/12/1
N2 - Established electrodecarboxylative etherification protocols are based on Hofer-Moest-type reaction pathways. An oxidative decarboxylation gives rise to radicals, which are further oxidised to carbocations. This is possible only for benzylic or otherwise stabilised substrates. Here, we report the electrodecarboxylative radical-radical coupling of lithium alkylcarboxylates with 1-hydroxybenzotriazole at platinum electrodes in methanol/pyridine to afford alkyl benzotriazole ethers. The substrate scope of this electrochemical radical coupling extends to primary and secondary alkylcarboxylates. The benzotriazole products easily undergo reductive cleavage to the alcohols. They can also serve as synthetic hubs to access a wide variety of functional groups. This reaction prototype demonstrates that electrodecarboxylative C–O bond formation can be taken beyond the intrinsic substrate limitations of Hofer-Moest mechanisms.
AB - Established electrodecarboxylative etherification protocols are based on Hofer-Moest-type reaction pathways. An oxidative decarboxylation gives rise to radicals, which are further oxidised to carbocations. This is possible only for benzylic or otherwise stabilised substrates. Here, we report the electrodecarboxylative radical-radical coupling of lithium alkylcarboxylates with 1-hydroxybenzotriazole at platinum electrodes in methanol/pyridine to afford alkyl benzotriazole ethers. The substrate scope of this electrochemical radical coupling extends to primary and secondary alkylcarboxylates. The benzotriazole products easily undergo reductive cleavage to the alcohols. They can also serve as synthetic hubs to access a wide variety of functional groups. This reaction prototype demonstrates that electrodecarboxylative C–O bond formation can be taken beyond the intrinsic substrate limitations of Hofer-Moest mechanisms.
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U2 - 10.1038/s41467-020-18275-1
DO - 10.1038/s41467-020-18275-1
M3 - Article
C2 - 32879323
AN - SCOPUS:85090088723
VL - 11
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
IS - 1
M1 - 4407
ER -