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Synthesis of C2-Symmetric Bisamidines:  A New Type of Chiral Metal-Free Lewis Acid Analogue Interacting with Carbonyl Groups

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posted on 20.07.2007, 00:00 authored by Deniz Akalay, Gerd Dürner, Jan W. Bats, Michael Bolte, Michael W. Göbel
The chiral bisamidine 5 has been prepared in just two steps from malonodinitrile. In the monocationic form this compound adopts a planar conformation with an almost convergent orientation of two N−H groups. Ketones, aldehydes, and nitro compounds are assumed to bind to this strongly polar cleft via hydrogen bonds, resulting in a Lewis-acid-like activation of the carbonyl groups. A broad scope of reactions (Diels−Alder, hetero-Diels−Alder, Friedel−Crafts) can be catalyzed. The observed accelerations surpass the rate effects of neutral hydrogen-bond donors such as thioureas or TADDOLs.