Unveiling Novel Synthetic Pathways through Brook Rearrangement

Dedicated to Professor Amos B Smith, III

Abstract

The Brook rearrangement is a valuable synthetic tool that facilitates the controlled construction of complex molecules. Conventionally, it generates carbanion intermediates utilized in subsequent functionalization reactions. In this review, we will explore recent advancements in the Brook rearrangement that extend beyond the traditional functionalization reactions. Specifically, we will highlight its involvement in unusual bond cleavage, annulation reactions, and dearomatization efforts. The novelty of this rearrangement is underscored by showcasing its most recent applications.

1 Introduction

2 Novel Synthetic Pathways Involving the Brook Rearrangement

2.1 C–C and C–X Bond Formation

2.2 C–C and C–X Bond Cleavage

2.3 Stereodefined Substituted Silyl Enol and Allenol Ethers

2.4 Annulation Reactions

2.5 Dearomatization

3 Synthetic Applications

4 Conclusion

Key words

Brook rearrangement - anion relay chemistry - silyl migration - synthetic methods - complex molecules

Publication History

Received: 16 January 2024

Accepted after revision: 30 January 2024

Accepted Manuscript online:
30 January 2024

Article published online:
19 February 2024

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