A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with 
α‐Stannyl α‐Diazoacetate. "Stereoretentive" Stille Coupling with Formation of 
Chiral Quarternary Carbon Centers

Caló, Fabio P.; Fürstner, Alois

doi:10.1002/anie.202004377

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A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. "Stereoretentive" Stille Coupling with Formation of Chiral Quarternary Carbon Centers

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Caló, Fabio P.
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fürstner, Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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anie202004377-s1-supporting_information_renamed_b260e.pdf
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Citation

Caló, F. P., & Fürstner, A. (2020). A Heteroleptic Dirhodium Catalyst for Asymmetric Cyclopropanation with α‐Stannyl α‐Diazoacetate. "Stereoretentive" Stille Coupling with Formation of Chiral Quarternary Carbon Centers. Angewandte Chemie International Edition, 59(33), 13900-13907. doi:10.1002/anie.202004377.

Cite as: https://hdl.handle.net/21.11116/0000-0006-DB1A-7

Abstract

The heteroleptic dirhodium paddlewheel catalyst 7 with a chiral carboxylate/acetamidate ligand sphere is uniquely effective in asymmetric [2+1] cycloadditions with α‐diazo‐α‐trimethylstannyl (silyl, germyl) acetate. Originally discovered as a trace impurity in a sample of the homoleptic parent complex [Rh₂((R)‐TPCP)₄] (5), it is shown that the protic acetamidate ligand is quintessential for rendering 7 highly enantioselective. The –NH group is thought to lock the ensuing metal carbene in place via interligand hydrogen bonding. The resulting stannylated cyclopropanes undergo “stereoretentive” cross coupling, which shows for the first time that chiral quarternary carbon centers can be made by the Stille‐Migita reaction.