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Synthesis 2012(4): 489-503  
DOI: 10.1055/s-0031-1290158
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Transition-Metal-Catalyzed Enantioselective Propargylic Substitution Reactions of Propargylic Alcohol Derivatives with Nucleophiles

Yoshiaki Nishibayashi*
Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan
Fax: +81(3)58411175; e-Mail: ynishiba@sogo.t.u-tokyo.ac.jp;
Further Information

Publication History

Received 2 November 2011
Publication Date:
16 January 2012 (online)

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Abstract

Recent advances in the transition-metal-catalyzed enantioselective propargylic substitution reactions of propargylic alcohol derivatives with nucleophiles are reviewed in this article. After the disclosure of the first example of a ruthenium-catalyzed propargylic alkylation, various types of enantioselective propargylic substitution reactions, including enantioselective propargylation of aromatic compounds, have been reported in the last eight years. In addition, a variety of enantioselective propargylic alkylations use two distinct catalysts, where the two catalysts work cooperatively to promote the asymmetric reactions.

1 Introduction

2 Ruthenium-Catalyzed Enantioselective Propargylic Substitution Reactions

2.1 Propargylic Alkylation

2.2 Propargylation of Aromatic Compounds with Propargylic Alcohols

2.3 Propargylic Substitution Reactions of Propargylic Alcohols with Alkenes

2.4 Cycloadditions between Propargylic Alcohols and 2-Naphthols

3 Copper-Catalyzed Enantioselective Propargylic Substitution Reactions

3.1 Propargylic Amination

3.2 Ring-Opening Reactions of Ethynyl Epoxides

3.3 Propargylic Alkylation

3.4 Propargylation of Indoles

4 Cooperative Enantioselective Propargylic Alkylations ­Using Transition-Metal Catalysts and Organocatalysts

4.1 With Ruthenium Catalysts

4.2 With Copper Catalysts

4.3 With Lewis Acid Catalysts

5 Cooperative Reactions Using Distinct Transition-Metal Catalysts

6 Miscellaneous Reactions

7 Conclusion

Key words

alkylation - enantioselective reaction - nucleophile - organocatalyst - propargylic alcohol - propargylic substitution reaction

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