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Synthesis 2019; 51(13): 2729-2736
DOI: 10.1055/s-0037-1611519
DOI: 10.1055/s-0037-1611519
paper
Gold(III)/Sodium Diphenylphosphinobenzene-3-sulfonate (TPPMS) Catalyzed Dehydrative N-Benzylation of Electron-Deficient Anilines in Water
This work was supported by JSPS KAKENHI Grant Number 16K08179.Further Information
Publication History
Received: 22 February 2019
Accepted after revision: 26 March 2019
Publication Date:
17 April 2019 (online)
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.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611519.
- Supporting Information
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For solvent-free conditions, see:
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For copper-catalyzed dehydrative coupling reactions, see:
For cobalt-catalyzed dehydrative coupling reactions, see: