Gold(III)/Sodium Diphenylphosphinobenzene-3-sulfonate (TPPMS) Catalyzed Dehydrative N-Benzylation of Electron-Deficient Anilines in Water

Hidemasa Hikawa; Mika Matsumoto; Sayoko Tawara; Shoko Kikkawa; Isao Azumaya

doi:10.1055/s-0037-1611519

Synthesis, Table of Contents

Synthesis 2019; 51(13): 2729-2736
DOI: 10.1055/s-0037-1611519

paper

Gold(III)/Sodium Diphenylphosphinobenzene-3-sulfonate (TPPMS) Catalyzed Dehydrative N-Benzylation of Electron-Deficient Anilines in Water

Hidemasa Hikawa *

,

Mika Matsumoto

,

Sayoko Tawara

,

Shoko Kikkawa

,

Isao Azumaya *

Faculty of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan Email: hidemasa.hikawa@phar.toho-u.ac.jp Email: isao.azumaya@phar.toho-u.ac.jp

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Abstract

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Abstract

A strategy for the dehydrative N-benzylation of electron-deficient anilines in water has been developed. The gold(III)/sodium diphenylphosphinobenzene-3-sulfonate (TPPMS) catalyst is highly effective as a Lewis acid for the activation of alcohols and tolerates aerobic conditions. A Hammett study in the reaction of para-substituted benzhydryl alcohols shows negative σ values, indicating a build-up of cationic charge during the rate-determining sp³ C–O bond-cleavage step. The inverse kinetic solvent isotope effect (KSIE = 0.6) is consistent with a specific acid catalysis mechanism. This simple protocol can be performed under mild conditions in an atom-economic process without the need for base or other additives, furnishing the electron-deficient N-benzylic anilines in moderate to excellent yields along with water as a sole coproduct.

Key words

gold - water - benzylic alcohol - aniline - N-benzylation

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References

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