Mesomeric Betaines and N-Heterocyclic Carbenes of Pyrazole and Indazole

Andreas Schmidt; Zong Guan

doi:10.1055/s-0032-1316787

Synthesis, Table of Contents

Synthesis 2012; 44(21): 3251-3268
DOI: 10.1055/s-0032-1316787

review

Mesomeric Betaines and N-Heterocyclic Carbenes of Pyrazole and Indazole

Andreas Schmidt*

Clausthal University of Technology, Institute of Organic Chemistry, Leibnizstr. 6, 38678 Clausthal-Zellerfeld, Germany Fax: +49(5323)722834 Email: schmidt@ioc.tu-clausthal.de

,

Zong Guan

Clausthal University of Technology, Institute of Organic Chemistry, Leibnizstr. 6, 38678 Clausthal-Zellerfeld, Germany Fax: +49(5323)722834 Email: schmidt@ioc.tu-clausthal.de

› Author Affiliations

Abstract

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Abstract

The chemistry of the N-heterocyclic carbenes pyrazol-3-ylidene and indazol-3-ylidene, and of the remote N-heterocyclic carbene pyrazol-4-ylidene, is reviewed. Heterocumulene adducts of pyrazol- and indazol-3-ylidene are pseudo-cross-conjugated heterocyclic mesomeric betaines, from which the corresponding N-heterocyclic carbenes can be generated by thermal cleavage of the carbene–heterocumulene bond. Cross-conjugated heterocyclic mesomeric betaines such as pyrazolium-4-carboxylates are formal 1:1 adducts of the heterocumulene carbon dioxide with the remote N-heterocyclic carbene pyrazol-4-ylidene. These relationships give rise to an interesting interplay between the two compound classes, N-heterocyclic carbenes and heterocyclic mesomeric betaines.

1 Introduction

2 Classifications

2.1 Mesomeric Betaines of Pyrazole and Indazole

2.2 N-Heterocyclic Carbenes and Relatives of Pyrazole and Indazole

3 Conjugated Mesomeric Betaines of Pyrazole and Indazole

4 Ylides of Pyrazole

5 Cross-Conjugated Mesomeric Betaines and Remote N-Heterocyclic Carbenes of Pyrazole (Pyrazol-4-ylidenes)

6 Pseudo-Cross-Conjugated Mesomeric Betaines and N-Heterocyclic Carbenes of Pyrazole (Pyrazol-3-ylidenes)

7 Pseudo-Cross-Conjugated Mesomeric Betaines and N-Heterocyclic Carbenes of Indazole (Indazol-3-ylidenes)

8 Conclusions

Key words

mesoion - pyrazol-4-ylidene - pyrazol-3-ylidene - indazol-3-ylidene - carbene complex - catalysis - cyclic bent allene - abnormal N-heterocyclic carbene - remote N-heterocyclic carbene

Full Text

References

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