Synthesis 2010(12): 1929-1982  
DOI: 10.1055/s-0029-1218801
© Georg Thieme Verlag Stuttgart ˙ New York

Chiral Phosphoric Acids as Versatile Catalysts for Enantioselective Transformations

Masahiro Terada*
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
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Further Information

Publication History

Received 25 March 2010
Publication Date:
27 May 2010 (online)


Chiral phosphoric acids derived from axially chiral biaryls and related chiral Brønsted acids have emerged as an attractive and widely applicable class of enantioselective organocatalysts for a variety of organic transformations. This review focuses on recent achievements in the development of enantioselective transformations using these axially chiral phosphoric acids and their analogues as chiral Brønsted acid catalysts. The contents are arranged according to the specific types of carbon-carbon bond-forming reactions, followed by carbon-heteroatom bond-forming reactions and functional group transformations, including reduction and oxidation. Further applications to combined phosphoric acid and metal complex catalytic systems and new aspects in the development of chiral Brønsted acid catalysts are also highlighted.

1 Introduction

2 Chiral Phosphoric Acids as Enantioselective Brønsted Acid Catalysts

3 Mannich and Related Reactions

4 One-Carbon Homologation Reactions via Activation of Imines

5 Friedel-Crafts and Related Reactions

6 Ene (Type) Reactions

7 Cycloaddition Reactions

8 Cyclization Reactions

9 Transformations via Protonation of Electron-Rich Double Bonds

10 Miscellaneous Carbon-Carbon Bond-Forming Reactions

11 Carbon-Heteroatom Bond-Forming Reactions

12 Transfer Hydrogenation Reactions

13 Oxidations

14 Combined Use of Metal Complex and Phosphoric Acid Catalysts

15 New Aspects in the Development of Chiral Brønsted Acid Catalysts

16 Conclusions


The double hydrogen bonding model of the TS structure has been proposed in the aza-ene type reaction of glyoxylate 124 with enecarbamate 105, see ref. 97.