Gold-catalyzed heterogeneous aerobic dehydrogenative amination of α,β-unsaturated aldehydes to enaminals

Xiongjie Jin; Kazuya Yamaguchi; Noritaka Mizuno

doi:10.1002/anie.201308260

Gold-catalyzed heterogeneous aerobic dehydrogenative amination of α,β-unsaturated aldehydes to enaminals

Angew Chem Int Ed Engl. 2014 Jan 7;53(2):455-8. doi: 10.1002/anie.201308260. Epub 2013 Nov 29.

Authors

Xiongjie Jin¹, Kazuya Yamaguchi, Noritaka Mizuno

Affiliation

¹ Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan).

PMID: 24288168
DOI: 10.1002/anie.201308260

Abstract

Although enaminals (β-enaminals) are very important compounds and have been utilized as useful synthons for various important compounds, they have been synthesized through non-green and/or limited procedures until now. Herein, we have successfully developed a green synthetic procedure using a heterogeneous catalyst. In the presence of gold nanoparticles supported on manganese-oxide-based octahedral molecular sieves OMS-2 (Au/OMS-2), dehydrogenative amination of α,β-unsaturated aldehydes with amines proceeded efficiently, with the corresponding enaminals isolated in moderate to high yields (50-97 %). The catalysis was truly heterogeneous, and Au/OMS-2 could be reused. Furthermore, the formal Wacker-type oxidation of α,β-unsaturated aldehydes to enaminones has been realized.

Keywords: aldehydes; amines; dehydrogenative amination; gold; heterogeneous catalysis.