What is it about?

Magnesium cyclopropylidenoids are generally known for their electrophilic and carbene-like reactivity. In this study, we demonstrated that they can also function as nucleophiles. We successfully generated a Magnesium　cyclopropylidenoid bearing an electrophilic carbonate group within the same molecule, creating a functionalized organomagnesium intermediate that undergoes efficient intramolecular cyclization to produce cyclopropane-fused α-chlorolactones. The strategy also enables highly enantioselective synthesis of optically active products.

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Why is it important?

This work expands the fundamental understanding of magnesium carbenoid chemistry by revealing an underexplored nucleophilic reaction pathway. It also demonstrates that organomagnesium intermediates can be generated even in the presence of an electrophilic carbonate group, providing a new example of a functionalized organomagnesium reagent. These findings open new possibilities for designing chemoselective reactions and constructing complex cyclopropane-containing molecules.

Perspectives

Most applications of magnesium carbenoids have relied on their electrophilic or carbene-like behavior. Our results show that their nucleophilic character can also be exploited in synthetic chemistry. More broadly, the successful preparation of a functionalized magnesium carbenoid containing an electrophilic group suggests that similarly designed organomagnesium intermediates could unlock many new selective transformations and ring-forming reactions.

Associate Professor Tsutomu Kimura

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This page is a summary of: Synthesis of cyclopropane-fused α-chlorolactones utilizing the nucleophilicity of cyclopropylmagnesium carbenoids, Tetrahedron Letters, February 2014, Elsevier,
DOI: 10.1016/j.tetlet.2014.01.038.
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