American Chemical Society
jo6b02056_si_001.pdf (10.78 MB)

Electroreductive Intermolecular Coupling of Coumarins with Benzophenones: Synthesis of 4‑(2-Hydroxyphenyl)-5,5-diaryl-γ-butyrolactones, 2‑(2,2-Diaryl-2,3-dihydrobenzofuran-3-yl)acetic Acids, and 4‑(Diarylmethyl)coumarins

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journal contribution
posted on 2016-10-05, 00:00 authored by Naoki Kise, Yusuke Hamada, Toshihiko Sakurai
The electroreductive coupling of coumarins with benzophenones in the presence of TMSCl gave adducts reacted at the 4-position of coumarins as trimethylsilyl ethers. From 3-methylcoumarin, 3,4-cis-adducts were formed stereoselectively. The de-trimethylsilylation of the adducts with 1 M HCl aq or TBAF in THF at 25 °C produced 4-(2-hydroxyphenyl)-5,5-diaryl-γ-butyrolactones. The γ-butyrolactones were further transformed to 2-(2,2-diaryl-2,3-dihydrobenzofuran-3-yl)­acetic acids by treatment with 1 M HCl aq at reflux temperature. The de-trimethylsilylation of the adducts with 1 M HCl in MeOH afforded 2-(2,2-diaryl-2,3-dihydrobenzofuran-3-yl)­acetic acid methyl esters. The de-trimethylsiloxylation of the adducts or dehydration of the γ-butyrolactones brought about 4-(diarylmethyl)­coumarins.