Cyclisations of Organolithiums onto Aromatic Rings

Abstract

The synthesis of bicyclic and other polycyclic structures by intramolecular nucleophilic attack of organolithiums on aromatic rings is reviewed. This review begins with some early observations of cyclisation-rearomatisation reactions that suggested the possibility of using aromatic rings to trap organolithiums. More recent results have shown that anion-stabilising groups, particularly sulfur- or amide-containing functional groups, are able to retard the rearomatisation step and may lead to dearomatised products. Recent optimisation of such reactions, particularly those employing aromatic amides, has allowed them to be used as key steps in a number of syntheses of natural products and their analogues.

• 1 Organolithium Cyclisations

• 2 Dearomatising Organolithium Cyclisations

• 3 Dearomatising Cyclisations of Amides

• 3.1 Nitrogen Substituents

• 3.2 Alternatives to N-Benzyl Groups

• 3.3 Cyclisation of N-Benzoyl Oxazolidines

• 3.4 Cumyl as a Protecting Group

• 3.5 Functionalised Benzamides: Enones as Products

• 3.6 Avoiding HMPA: LDA as a Cyclisation Promoter

• 3.7 Asymmetric Cyclisation with Chiral Lithium Amides

• 3.8 Stereospecific Cyclisation of Chiral Benzamides

• 3.9 Cyclisation onto Pyrroles

• 3.10 Applications of the Dearomatising Cyclisation to the Synthesis of Kainoids

• 4 Cyclisation of Unstabilised Organolithiums onto Activated Naphthalene Rings

• 4.1 Oxazoline Activation

• 4.2 Sulfone Activation

• 4.3 Synthetic Application of the Dearomatising Cyclisation of Lithiated Naphthylsulfones

• 5 Summary

Key words

organolithium - anionic cyclisation - dearomatisation

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Beech C. P. Undergraduate project, University of Manchester, 1995.