Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran

Abstract

The cleavage of ethers is commonly encountered in organometallic chemistry, although rarely studied in the context of new, emerging bimetallic reagents. Recently, it was reported that a bimetallic sodium–zinc base can deprotonate cyclic tetrahydrofuran under mild conditions without opening its heterocyclic (OC4) ring. In marked contrast to this synergic sedation, herein we show that switching to the more reactive sodium–magnesium or sodium–manganese bases promotes cleavage of at least six bonds in tetrahydrofuran, but uniquely the ring fragments are captured in separate crystalline complexes. Oxide fragments occupy guest positions in bimetallic, inverse crown ethers and C4 fragments ultimately appear in bimetallated butadiene molecules. These results demonstrate the special synergic reactivity that can be executed by bimetallic reagents, which include the ability to capture and control, and thereby study, reactive fragments from sensitive substrates. Tetrahydrofuran can be unexpectedly cleaved by bimetallic sodium–magnesium and sodium–manganese bases. At least six bonds are broken in the one-pot reaction, but all fragments are separately captured to form crystalline compounds.

Cite this article

Mulvey, R., Blair, V., Clegg, W. et al. Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran. Nature Chem 2, 588–591 (2010). https://doi.org/10.1038/nchem.667

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