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Synthesis 2009(3): 339-368  
DOI: 10.1055/s-0028-1083325
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Intermolecular Addition Reactions of N-Acyliminium Ions (Part I) [¹]

Arife Yazici, Stephen G. Pyne*
School of Chemistry, University of Wollongong, Wollongong, NSW 2522, Australia
Fax: +61(2)42214987; e-Mail: spyne@uow.edu.au;
Further Information

Publication History

Received 22 September 2008
Publication Date:
26 January 2009 (online)

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Abstract

This review highlights the advances in the literature up to July 2008 on the intermolecular reactions of acyclic and cyclic N-acyliminium ions. This is an update of an earlier review in 2000 on this topic and does not include intramolecular addition reactions to N-acyliminium ions which was recently reviewed. This review is presented in two parts, with the first part dealing with acyclic and pyrrolidinone-based N-acyliminium ions. Part II continues with other five-membered heterocyclic derivatives and higher systems.

Part I

1 Introduction

2 Acyclic N-Acyliminium Ions

2.1 Synthesis of Acyclic N-Acyliminium Ion Precursors

2.2 Reactions of Acyclic N-Acyliminium Ions

2.2.1 Reactions with Nucleophiles

2.2.1.1 Silicon-Based Nucleophiles

2.2.1.2 Aromatic Nucleophiles

2.2.1.3 Organostannanes

2.2.1.4 Organometallic Reagents

2.2.1.5 Thiols

2.2.1.6 Alkenes

2.2.1.7 Nitrogen Nucleophiles

2.2.1.8 Alkyl Radicals

2.2.2 Cycloaddition Reactions

2.2.3 Cationic Carbohydroxylation Reactions

3 Cyclic N-Acyliminium Ions

3.1 Synthesis of Cyclic N-Acyliminium Ion Precursors

3.1.1 Preparation of Iminium Ions in situ by Anodic Oxidation

3.2 Five-Membered-Ring N-Acyliminium Ions

3.2.1 Reactions of Pyrrolidinone-Based N-Acyliminium Ions

3.2.1.1 Silicon-Based Nucleophiles

3.2.1.2 Aromatic Nucleophiles

3.2.1.3 Organostannanes

3.2.1.4 Organometallic Reagents

3.2.1.5 Active Methylene Compounds

3.2.1.6 Nitrile Nucleophiles (Ritter Reaction)

Part II

3.2.2 Reactions of N-Acylpyrrolidine-Based N-Acyliminium Ions with Nucleophiles

3.2.3 Reactions of Oxazolidinone-Based N-Acyliminium Ions with Nucleophiles

3.2.4 Cyclocondensation Reaction of N-Aminidinyl Iminium Ions

3.3 Reactions of Six-Membered-Ring N-Acyliminium Ions

3.3.1 Reactions of Piperidinone-Based N-Acyliminium Ions with Nucleophiles

3.3.3 Reactions of Piperazine-Based N-Acyliminium Ions with Nucleophiles

3.3.4 Reactions of Pyridine-Based N-Acyliminium Ions with Nucleophiles

3.3.5 Reactions of N,O-Acetal Oxathiazinane N-Sulfonyliminium Ions with Nucleophiles

3.4 Reactions of Seven-Membered-Ring N-Acyliminium Ions

3.4.1 Reactions with Silicon-Based Nucleophiles

3.4.2 Cycloaddition Reactions

3.5 Reactions of Bicyclic N-Acyliminium Ions

3.5.1 Reactions with Nucleophiles

3.5.2 Cycloaddition Reactions

3.6 Other Systems

3.6.1 Silicon-Based Nucleophiles

4 Stereochemical Outcomes

5 Conclusions

Key words

N-acyliminium ion - nucleophilic addition - cycloaddition - aromatic electrophilic substitution - radical addition - peptides - pyrrolidines - piperidines