Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity

Autor:	R. Morris Bullock, Amy L. Speelman, Benjamin D. Neisen, Ba L. Tran, Thilina Gunasekara, Eric S. Wiedner
Rok vydání:	2020
Předmět:	chemistry.chemical_classification Ketone 010405 organic chemistry Hydride Dimer General Medicine General Chemistry 010402 general chemistry 01 natural sciences Aldehyde Catalysis 0104 chemical sciences chemistry.chemical_compound Monomer chemistry Amide Polymer chemistry Electrophile Proton NMR
Zdroj:	Angewandte Chemie International Edition. 59:8645-8653
ISSN:	1521-3773 1433-7851
DOI:	10.1002/anie.201916406
Popis:	We report mechanistic studies on the insertion reactions of [(NHC)Cu(μ-H)]2 complexes with carbonyl substrates by UV-vis and 1 H NMR spectroscopic kinetic studies, H/D isotopic labelling, and X-ray crystallography. The results of these comprehensive studies show that the insertion of Cu-H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu-H monomer from Cu-H dimer for more electrophilic substrates, and hydride transfer from a transient Cu-H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu-hemiacetalate and Cu-hemiaminalate moieties from the insertion of an ester or amide into the Cu-H bond.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::439c044ab9b4c29eee1ec3e7d2c99815 https://doi.org/10.1002/anie.201916406 Zobrazit plný text záznamu Plný text