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Recent developments in the Reformatsky-Claisen rearrangement
Jun Ishihara1, Susumi Hatakeyama
1Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan. jishi@nagasaki-u.ac.jp
Molecules (Basel, Switzerland)
|December 4, 2012
Summary
The Reformatsky-Claisen rearrangement, using zinc, offers a synthetic route. Recent advances, including indium mediation, expand its utility in organic synthesis.
Area of Science:
- Organic Chemistry
- Synthetic Methodology
- Reaction Mechanisms
Background:
- The Ireland-Claisen rearrangement is a well-established method for synthesizing natural products.
- The zinc-mediated Reformatsky-Claisen rearrangement is less explored compared to its Ireland-Claisen counterpart.
- Allyl a-bromoacetates are key substrates in these rearrangement reactions.
Purpose of the Study:
- To provide a comprehensive overview of recent developments in the Reformatsky-Claisen rearrangement.
- To highlight the potential and applications of zinc-mediated and other metal-mediated Reformatsky-Claisen reactions.
- To introduce a novel indium-mediated Reformatsky-Claisen rearrangement.
Main Methods:
- Review of existing literature on Reformatsky-Claisen and Ireland-Claisen rearrangements.
- Detailed examination of metal-mediated reaction conditions, particularly using zinc and indium.
- Analysis of substrate scope and reaction efficiency for various Reformatsky-Claisen variants.
Main Results:
- The Zn-mediated Reformatsky-Claisen rearrangement has shown promise but remains underutilized.
- Recent advancements have expanded the scope and efficiency of Reformatsky-Claisen type reactions.
- A newly developed In-mediated Reformatsky-Claisen rearrangement offers a novel synthetic pathway.
Conclusions:
- The Reformatsky-Claisen rearrangement, particularly metal-mediated variants, represents a valuable tool in organic synthesis.
- Further exploration of indium and other metal-mediated approaches is warranted.
- These rearrangements contribute to the efficient construction of complex organic molecules.
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