Asymmetric Syntheses of Oxindole
and Indole Spirocyclic Alkaloid Natural Products

Barry M. Trost; Megan K. Brennan

doi:10.1055/s-0029-1216975

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Synthesis 2009(18): 3003-3025
DOI: 10.1055/s-0029-1216975

REVIEW

Asymmetric Syntheses of Oxindole and Indole Spirocyclic Alkaloid Natural Products

Barry M. Trost*, Megan K. Brennan
Department of Chemistry, Stanford University, Stanford, CA 94305, USA
Fax: +1(650)7250002; e-Mail: bmtrost@stanford.edu;

Further Information

Publication History

Received 9 April 2009
Publication Date:
28 August 2009 (online)

Abstract
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Abstract

This review highlights the advances in the literature up to May 2009 in the synthesis of spirocyclic indoline natural products. The focus is on formation of the spirocyclic chiral center, including both enantioselective and diastereoselective methods. This review is split into two main sections, the first consisting of the formation of spirooxindoles and their application towards oxindole alkaloids, and the second covering asymmetric synthesis of spiroindoline natural products.

1 Introduction

2 Spirooxindole Alkaloids

2.1 Oxidative Rearrangements

2.2 Azomethine Ylide Cycloaddition

2.3 Asymmetric Addition-Elimination

2.4 Palladium-Catalyzed Heck Reactions

2.5 Palladium-Catalyzed Allylic Alkylation

2.6 Ring Expansion

2.7 Mannich Reaction

3 Spiroindoline Alkaloids

3.1 Palladium Catalyzed Asymmetric Allylic Alkylation

3.2 [4+2] Cycloaddition

3.3 Oxidative Rearrangement

3.4 Diastereoselective Pummerer Rearrangement

3.5 Tandem Iminium Cascade

3.6 Fischer Indole Synthesis

3.6.1 Diastereoselective Ring-Closing Metathesis

3.6.2 Diastereoselective Alkylation of Chiral Lactams

3.6.3 Regioselective Schmidt Reaction

3.6.4 Diastereoselective Ketene Lactonization

3.6.5 Harley-Mason Reaction

3.6.6 S_N2-Type Indole Alkylation

3.6.7 Aza-Cope-Mannich Rearrangement

4 Conclusion

Key words

alkaloids - spiro compounds - indoles - asymmetric synthesis - natural products

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These compounds are easily prepared in more than 90% yield from the corresponding 1-morpholino-2-nitroolefins and (S)-2-(methoxymethyl)pyrrolidine in methanol.