Enantioselective Friedel-Crafts Aminoalkylation Catalyzed by Chiral Ammonium 1,1′-Binaphthyl-2,2′-disulfonates

Abstract

A catalytic enantioselective Friedel-Crafts aminoalkylation between aromatic aldimines and N-benzylpyrrole with the use of a homogeneous chiral ammonium salt, (R)-BINSA-N,N-dimethylbutylamine, as a dynamic Brønsted acid-Brønsted base catalyst, is reported. Unlike the results with conventional catalysts, remarkably high reactivity was established at -78 ˚C within 30 minutes, and the corresponding aryl(1H-pyrrol-2-yl)methanamines were obtained with good to high enantioselectivities.

ammonium salt - Friedel-Crafts reaction - 1,1′-binaphthyl-2,2′-disulfonic acid (BINSA) - chiral Brønsted acid - organocatalyst

References and Notes

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<A NAME="RY03511ST-8">8</A>

With regard to other solvents, THF and propionitrile showed low enantioselectivities, and the catalysts showed poor solubility in Et₂O, n-hexane, and toluene.

<A NAME="RY03511ST-9">9</A>

Naturally abundant Na⁺ might be included during the analysis.

<A NAME="RY03511ST-10">10</A>

See the Supporting Information for details.

<A NAME="RY03511ST-11">11</A>

The optimum ratio of 4k to (R)-BINSA (1:1), which was examined in entries 11-13 in Table  [¹] , suggests that a monomeric (R)-BINSA-4k-1a complex is one of the most likely structures.