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Synthesis 2012(3): 351-361  
DOI: 10.1055/s-0031-1289668
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Recent Developments in Palladium-Catalyzed Alkene Aminoarylation Reactions for the Synthesis of Nitrogen Heterocycles

Danielle M. Schultz, John P. Wolfe*
Department of Chemistry, University of Michigan, 930 N. University Avenue, Ann Arbor, MI 48109-1055, USA
Fax: +1(734)6153790; e-Mail: jpwolfe@umich.edu;
Further Information

Publication History

Received 10 November 2011
Publication Date:
16 January 2012 (online)

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Abstract

This short review describes new developments in palladium-catalyzed aminoarylation reactions between aryl halides and alkenes bearing pendant nitrogen nucleophiles. These transformations provide a novel and powerful method for accessing numerous three-, five-, six-, and seven-membered nitrogen heterocycles.

1 Introduction

2 Synthesis of Pyrrolidines via Palladium-Catalyzed Alkene Aminoarylation Reactions

2.1 Palladium(0)-Catalyzed Alkene Aminoarylation Reactions

2.1.1 Synthesis of trans-2,5-Disubstituted Pyrrolidines

2.1.2 Transformations of Aryl Chloride Electrophiles

2.1.3 Synthesis of Hexahydro-3H-pyrrolizin-3-ones

2.1.4 Enantioselective Synthesis of Monosubstituted Pyrrolidines

2.1.5 Asymmetric Total Synthesis of (+)-Aphanorphine

2.2 Palladium(II)-Catalyzed Arene C-H Activation/Alkene Aminoarylation

3 Synthesis of Other Five-Membered Heterocycles via Palladium-Catalyzed Alkene Aminoarylation

3.1 Synthesis of Pyrazolidines

3.2 Synthesis of Isoxazolidines

4 Aminoarylation Reactions for the Synthesis of Three-, Six-, and Seven-Membered Heterocycles

4.1 Synthesis of Aziridines

4.2 Synthesis of Morpholines

4.3 Synthesis of Saturated 1,4-Benzodiazepines

5 Palladium-Catalyzed Synthesis of Fused-, Bridged-, and Spiro-Polycyclic Heterocycles

5.1 Cascade Alkene Difunctionalization Reactions

5.2 Tandem N-Arylation/Alkene Aminoarylation Reactions

5.3 Intramolecular Alkene Aminoarylation Reactions

5.3.1 Synthesis of Tropane Derivatives

5.3.2 Synthesis of Spirooxindoles

5.3.3 Cascade C-H Functionalization/Intramolecular Alkene Aminoarylation Reactions

6 Conclusions

Key words

alkenes - amines - arylation - catalysis - heterocycles - palladium­ - stereoselective synthesis

23

Pyrrolidine-forming reactions of substrates bearing homo­-allylic substituents proceed with low diastereoselectivity. See references 1a,b and 7.