N-Heterocyclic Carbene Ligand-Controlled Chemodivergent Suzuki–Miyaura Cross Coupling
Year: 2019
Type: article
Abstract: Two N-heterocyclic carbene ligands provide orthogonal chemoselectivity during the Pd-catalyzed Suzuki-Miyaura (SM) cross-coupling of chloroaryl triflates. The use of SIPr [SIPr = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene] leads to selective cross-coupling at chloride, while the use of SIMes [SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene] provides selective coupling at triflate. With most chloroaryl triflates and arylboronic acids, ligand-controlled selectivity is high (≥10:1). The scope of this methodology is significantly more general than previously reported methods for selective SM coupling of chloroaryl triflates using phosphine ligands. Density functional theory studies suggest that palladium's ligation state during oxidative addition is different with SIMes compared to SIPr.
Source: The Journal of Organic Chemistry
Institution: Montana State University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Funders: National Science Foundation, M.J. Murdock Charitable Trust, University of Montana, Montana State University, San Diego Supercomputer Center, National Institutes of Health, National Institute of General Medical Sciences, Division of Chemistry, Division of Biological Infrastructure, Division of Advanced Cyberinfrastructure
Awards: G114976773, G1310521215, G1400945677, G1640737532, G1742171491, G179862484, G1942859959, G2017798065, G2206590661, G2523737452, G2909499646, G3147773666, G3226045097, XSEDE 2.0: Integrating, Enabling and Enhancing National Cyberinfrastructure with Expanding Community Involvement, G3902111948, G4072547516, G5135854252, MRI: Acquisition of a cryoprobe- and autosampler-equipped AVANCE III 500 MHz solution NMR, G5986892838, REU Site: Mountains and Minds: New Chemical Insights Into Biology, G6056929667, G6401591588, MRI: Acquisition of a Small Molecule Single Crystal X-ray Diffractometer for Research and Education Across Montana, G6648061574, G6671297155, G7633065944, G7691771761, Biomolecular Structure and Dynamics, CAREER: Combined Experimental and Computational Approach to Controlling Site Selectivity in Cross Coupling Chemical Reactions
OpenAlex ID: W2972029020