Evans DA,
*,
Hoveyda AH.
Harvard University, Cambridge, USA
Samarium-Catalyzed Intramolecular Tishchenko Reduction of β-Hydroxy Ketones. A Stereoselective Approach to the Synthesis of Differentiated
anti 1,3-Diol Monoesters.
J. Am. Chem. Soc. 1990;
112: 6447-6449
Key words
reduction - stereoselective synthesis - 1,3-diols - Evans–Tishchenko reaction
Significance
1,3-Diols are ubiquitous in natural products and bioactive compounds. In 1990, the Evans group reported a highly diastereoselective reduction of β-hydroxy ketones to access anti-1,3-diol monoesters. Importantly, this transformation exhibits wide functional group tolerance and operates under very mild conditions. This has led to its widespread adoption in total syntheses (see Review below).
Review
K. J. Ralston, A. N. Hulme Synthesis
2012, 44, 2310–2342.
Comment
In the Fürstner synthesis of the formosalides they utilized the Evans–Tishchenko reaction to set a crucial anti-1,3-diol. Interestingly, they also observed an acyl transfer in low yield; this transfer was also found when using this reaction on epimeric starting materials to probe the stereochemistry of the formosalides.
