“Sandwich” Diimine-Copper Catalysts for C−H Functionalization by Carbene Insertion
Dr. Kristine Klimovica
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Houston, TX, USA
Search for more papers by this authorDr. Julius X. Heidlas
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Houston, TX, USA
Search for more papers by this authorIrvin Romero
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Houston, TX, USA
Search for more papers by this authorThanh V. Le
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Houston, TX, USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Olafs Daugulis
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Houston, TX, USA
Search for more papers by this authorDr. Kristine Klimovica
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Houston, TX, USA
Search for more papers by this authorDr. Julius X. Heidlas
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Houston, TX, USA
Search for more papers by this authorIrvin Romero
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Houston, TX, USA
Search for more papers by this authorThanh V. Le
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Houston, TX, USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Olafs Daugulis
Department of Chemistry, University of Houston, 3585 Cullen Blvd., Houston, TX, USA
Search for more papers by this authorGraphical Abstract
A new catalyst platform for C(sp3)−H bond functionalization has been discovered. “Sandwich” diimine-copper(I) complexes catalyze reactions of alkane, ether, and amine C−H bonds with a large panel of diazo compounds. Additionally, the first metal-catalyzed C(sp3)−H methylation by CH2N2 is disclosed. The electrophilicity and extreme steric bulk of these catalysts are likely reasons for their efficiency.
Abstract
We report here “sandwich” diimine-copper(I) catalysts for C(sp3)−H bond functionalization. Reactions of alkanes and ethers with trimethylsilyldiazomethane, ethyl diazoacetate, and trifluoromethyl-diazomethane have been demonstrated. We also report C(sp3)−H bond methylation, benzylation, and diphenylmethylation by diazomethane, aryldiazomethanes, and diphenyldiazomethane. These reactions are rare examples of base-metal catalyzed, intermolecular C(sp3)−H functionalizations by employing unactivated diazo compounds. Electrophilicity and unique steric environment of “sandwich”-copper catalysts are likely reasons for their catalytic efficiency.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Supporting Information
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