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Synthesis 2010(22): 3785-3801  
DOI: 10.1055/s-0030-1258296
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Highly Practical BINOL-Derived Acid-Base Combined Salt Catalysts for the Asymmetric Direct Mannich-Type Reaction

Manabu Hatanoa, Kazuaki Ishihara*a,b
a Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya, 464-8603, Japan
b 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;
Further Information

Publication History

Received 17 September 2010
Publication Date:
14 October 2010 (online)

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Abstract

The catalytic asymmetric direct Mannich-type reaction between aldimines and 1,3-dicarbonyl compounds is one of the most important carbon-carbon bond-forming reactions in organic chemistry. The resulting Mannich adducts can be efficiently transformed into pharmaceutically useful, optically active β-amino ketones, β-amino esters, β-lactams, etc. In the course of our study of chiral acid-base combined salt catalysts for asymmetric reactions, we developed a series of simple, practical, chiral BINOL-derived salt catalysts, such as chiral pyridinium 1,1′-binaphthyl-2,2′-disulfonates 1, chiral lithium(I) binaphtholate 2, chiral magnesium(II) binaphtholate (3), chiral calcium(II) phosphate 4, and chiral phosphoric acid 5, which were particularly effective for direct Mannich-type reactions.

1 Introduction

2 1,1′-Binaphthyl-2,2′-disulfonic Acid (BINSA)-Pyridinium Salts

3 Lithium(I) Binaphtholate Salts

4 Magnesium(II) Binaphtholate Salts

5 Calcium(II) Phosphate Salts and Chiral Phosphoric Acids

6 Conclusions

Key words

acid-base combined salt catalyst - aldimine - asymmetric catalysis - 1,3-dicarbonyl compound - direct Mannich-type reaction

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20

pK a values, which were reported in SciFinder, were calculated using Advanced Chemistry Development (ACD/Labs) software V11.02 (1994-2010 ACD/Labs).