Stereocontrolled Aldol-Like Reactions Involving Oxocarbenium Intermediates

Oxocarbenium cations are key intermediates for the stereocontrolled construction of carbon–carbon bonds. In particular, we have developed a wide range of stereoselective aldol-like processes that take advantage of the high reactivity of the oxocarbenium species arising from acetals, glycals, and ort...

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Bibliographic Details
Published in:Synlett 2024-08, Vol.35 (13), p.1500-1529
Main Authors: Galeote, Oriol, Kennington, Stuart C. D., Mellado-Hidalgo, Miguel, Costa, Anna M., Romea, Pedro, Urpí, Fèlix
Format: Article
Language:English
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Summary:Oxocarbenium cations are key intermediates for the stereocontrolled construction of carbon–carbon bonds. In particular, we have developed a wide range of stereoselective aldol-like processes that take advantage of the high reactivity of the oxocarbenium species arising from acetals, glycals, and orthoesters with metal enolates. This Account describes the development and optimization of such processes, together with other significant contributions, with a particular emphasis on their application to the synthesis of natural products. 1 Introduction 2 Substrate-Controlled Processes 2.1 Additions to Acyclic Acetals 2.2 Additions to Cyclic Acetals 3 Chiral-Auxiliary-Based Processes 3.1 Additions to Acyclic Acetals 3.2 Additions to Cyclic Acetals and Glycals 4 Chiral-Catalysis-Based Processes 4.1 Organocatalysis 4.2 Metal Catalysis 5 Conclusions
ISSN:0936-5214
1437-2096
DOI:10.1055/a-2184-5115