C-C bond activation as a new trigger for remote functionalizations Charlotte Teschers , Anthony Cohen and Ilan Marek Israel Institute of Technology, Israel Remote functionalizations have gained momentum as they enable the editing of functional groups at a distal position from the initial reactive site. [1] As part of our research campaign on chain-walking remote functionalization involving cyclopropane ring-opening reactions, [2] we envisioned to introduce cyclopropane C-C single bond activation as a new trigger for remote functionalizations. The design and synthesis of highly substituted cyclopropanols suitable to engage in this transformation are disclosed along with a brief optimization study for the Pd-catalyzed C-C activation – chain-walking transformation. Preliminary insights into scope and limitations support the proposed mechanism of initial β-carbon elimination from the palladium cyclopropoxide followed by chain-walking isomerization. This new transformation furnishes α-quaternary (di)aldehydes as valuable synthetic lynchpins.
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e) A. Cohen, J. Chagneau, I. Marek, ACS Catal. 2020 , 10 , 7154−7161; f) A. Cohen, A. Kaushansky, I. Marek, JACS Au 2022 , 2 , 687–696.
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