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Issue 29, 2016
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Cationic palladium(ii)-catalyzed dehydrative nucleophilic substitutions of benzhydryl alcohols with electron-deficient benzenethiols in water

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Abstract

An efficient direct nucleophilic substitution of benzhydryl alcohols with electron-deficient benzenethiols using cationic Pd(II) catalysts as Lewis acids in water is reported. Atom economical and environmentally benign protocols afford S-benzylated products in moderate to excellent yields. Commercially available Pd(MeCN)4(OTf)2, PdCl2(MeCN)2, and Na2PdCl4 are highly efficient catalysts. Notably, this simple protocol can be achieved without any other additives such as acids, bases, or external ligands. A Hammett study on the rate constants of S-benzylation by using various substituted benzhydryl alcohols yielded negative ρ values, suggesting that there is a build-up of positive charge in the transition state.

Graphical abstract: Cationic palladium(ii)-catalyzed dehydrative nucleophilic substitutions of benzhydryl alcohols with electron-deficient benzenethiols in water

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Publication details

The article was received on 26 May 2016, accepted on 24 Jun 2016 and first published on 24 Jun 2016


Article type: Paper
DOI: 10.1039/C6OB01140C
Org. Biomol. Chem., 2016,14, 7038-7045

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    Cationic palladium(II)-catalyzed dehydrative nucleophilic substitutions of benzhydryl alcohols with electron-deficient benzenethiols in water

    H. Hikawa, Y. Machino, M. Toyomoto, S. Kikkawa and I. Azumaya, Org. Biomol. Chem., 2016, 14, 7038
    DOI: 10.1039/C6OB01140C

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