A diverse array of highly functionalized 2-diazo-1,5-dicarbonyl compounds were formed by the Lewis acid-catalyzed reaction of enoxysilanes with β-hydroxy-α-diazo carbonyls. The active electrophile in this reaction is the little-studied and poorly understood vinyl diazonium salt, which is generated in situ by Zn(OTf)2-catalyzed dehydroxylation of β-hydroxy-α-diazo carbonyls. The vinyl diazonium is intercepted by the enoxysilane nucleophile before loss of N2 to give diazo-containing scaffolds with increased molecular complexity. The reaction appears to be general, and a variety of functional groups, including common protecting groups, are well tolerated. The 2-diazo-1,5-dicarbonyl products are formed in yields of up to 99% with diastereoselectivity up to &gt;20:1 in short order from simple starting materials. These products are easily derivatized into monocylic and bridged bicylic tetrahydrofurans containing up to 4 and 6 contiguous stereogenic centers, respectively.

Diastereoselective synthesis of functionalized 2-diazo-1,5-dicarbonyl compounds via Lewis acid catalysis

ACS Spring 2022

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