Ring-Closure Reactions of ortho-Vinyl-tert-anilines and (Di)Aza-Heterocyclic Analogues via the tert-Amino Effect: Recent Developments

Abstract

One version of the tert-amino effect operating in tert-anilines possessing an ortho-vinyl substituent affords a fused tetrahydropyridine ring by an isomerization process with the formation of a new carbon-carbon bond between the vinyl and tert-amino moieties. Since its discovery in 1984, this type of cyclization has been efficiently used for the construction of fused-ring systems. However, it has been found that the electron-deficient heterocyclic analogues of tert-anilines, such as diazines, may undergo isomerization at considerably lower reaction rates and, as a consequence, their reactions may require harsh conditions. Recent synthetic studies have indicated that the rate and yield may be improved by incorporating the β-vinylic carbon atom into an electron-deficient ring and/or buttressing the tert-amino group, and/or performing the reaction by means of microwave irradiation.

This review describes relatively recent synthetic transformations involving this type of tert-amino effect and devotes special attention to structure-reactivity relationships including regio- and stereo­chemical aspects.

• 1 Introduction

• 2 The tert-Amino Effect: Type 2 Reactions

• 2.1 Substrates with a Dicyanovinyl Group

• 2.1.1 Benzene Derivatives

• 2.1.2 Pyridine Derivatives

• 2.1.3 Pyrimidine Derivatives

• 2.1.4 Pyridazine Derivatives

• 2.2 Substrates with a Cyclic Vinyl Substituent

• 2.2.1 Pyridazine Derivatives

• 2.2.2 Pyrimidine Derivatives

• 2.2.3 Benzene Derivatives

• 2.3 Microwave-Assisted Synthesis

• 2.4 Regio- and Stereochemical Features

• 3 Conclusions

tert-amino effect - ring closure - isomerization - substituent effects - spiro compounds - heterocycles - microwave-assisted synthesis

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