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Synlett 2011(9): 1247-1250  
DOI: 10.1055/s-0030-1260538
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© Georg Thieme Verlag Stuttgart ˙ New York

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

Manabu Hatanoa, Yoshihiro Sugiuraa, Matsujiro Akakurab,c, Kazuaki Ishihara*a,c
a Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan
b Department of Chemistry, Aichi University of Education, Igaya-cho, Kariya 448-8542, Japan
c Japan Science and Technology Agency (JST), CREST, Furo-cho, Chikusa, Nagoya 464-8603, Japan
Fax: +81(52)7893222; e-Mail: ishihara@cc.nagoya-u.ac.jp;
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Publication History

Received 1 February 2011
Publication Date:
20 April 2011 (online)

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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.

Key words

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

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8

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

9

Naturally abundant Na+ might be included during the analysis.

10

See the Supporting Information for details.

11

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.