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Synlett 2009(12): 1905-1914  
DOI: 10.1055/s-0029-1217522
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Thieme Chemistry Journal Awardees - Where Are They Now? Triflic Imide Catalyzed Cycloaddition Reactions

Kiyosei Takasu*
Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8578, Japan
Fax: +81(75)7534610; e-Mail: kay-t@pharm.kyoto-u.ac.jp;
Further Information

Publication History

Received 14 January 2009
Publication Date:
01 July 2009 (online)

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Abstract

This Account summarizes our recent development of triflic imide (Tf2NH)-catalyzed cycloaddition and cascade reactions. Reactions of electron-rich olefins, possessing a silyl group, with α,β-unsaturated carbonyl compounds afforded highly substituted cyclobutanes, cyclopentanes, and bicyclo[4.2.0]octanes in good to excellent yields. In the reactions, Tf2NH acts as a precatalyst to produce a strong Lewis acid, silyl triflic imide, which activates the cycloaddition reactions. Reactions of electron-rich olefins with aldimines furnished highly substituted heterocycles such as piperidines, quinolines, and pyrrolidines. In these cases, Tf2NH acts as a strong Brønsted acid. Moreover, it was found that Tf2NH can catalyze more than two mechanistically distinct reactions in one pot (tandem catalysis), so that a variety of molecular skeletons can be constructed in a single operation.

1 Introduction

2 (2+2) Cycloaddition of α,β-Unsaturated Esters

2.1 (2+2) Cycloadditon with Silyl Enol Ethers

2.2 (2+2) Cycloaddition with Allylsilanes

3 (3+2) Cycloaddition of Donor-Acceptor Cyclopropanes

4 Multicomponent Reaction: Cascade (4+2)-(2+2) Cycloaddition

5 Cycloaddition of Imines

5.1 Aza-(4+2) Cycloaddition with 2-Siloxydienes

5.2 Cascade Povarov-Hydrogen-Transfer Reaction with Allylsilanes

5.3 Aza-(3+2) Cycloaddition with α,α-Dimethylallylsilanes

6 Conclusions

Key words

cycloadditions - catalysis - multicomponent reactions - triflic imides - auto-tandem catalysis

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2

Two systems of notations, (i+j+…) and [i+j+…], have been used for cycloaddition reactions; see the IUPAC guides for their difference. A (i+j+…) cycloaddition is a reaction in which two or more molecules provide units of i, j, … linearly connected atoms: these units become joined at their respective termini by new s bond so as to form a cyclic compound containing (i+j+…) atoms. In contrast, the symbolism [i+j+…] for a cycloaddition identifies the numbers i, j, … of electrons in the interacting units that participate in the transformation of reactants to products. In this Letter, the symbolism (i+j+…) will be used. See IUPAC Gold Book (http://goldbook.iupac.org/index.html).