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Ligand-Enabled β‑C(sp3)–H Olefination of Free Carboxylic Acids

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journal contribution
posted on 20.07.2018, 00:00 by Zhe Zhuang, Chang-Bin Yu, Gang Chen, Qing-Feng Wu, Yi Hsiao, Candice L. Joe, Jennifer X. Qiao, Michael A. Poss, Jin-Quan Yu
An acetyl-protected aminoethyl phenyl thioether has been developed to promote C­(sp3)–H activation. Significant ligand enhancement is demonstrated by the realization of the first Pd­(II)-catalyzed olefination of C­(sp3)–H bonds of free carboxylic acids without using an auxiliary. Subsequent lactonization of the olefinated product via 1,4 addition provided exclusively monoselectivity in the presence of multiple β-C–H bonds. The product γ-lactone can be readily opened to give either the highly valuable β-olefinated or γ-hydroxylated aliphatic acids. Considering the challenges in developing Heck couplings using alkyl halides, this reaction offers a useful alternative.