| Autor: |
Trammell, Rachel, D’Amore, Lorenzo, Cordova, Alexandra, Polunin, Pavel, Xie, Nan, Siegler, Maxime A., Belanzoni, Paola, Swart, Marcel, Garcia-Bosch, Isaac |
| Jazyk: |
angličtina |
| Rok vydání: |
2019 |
| Předmět: |
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| Popis: |
The use of copper for C-H bond functionalization, compared to other metals, is relatively unexplored. Herein, we report a synthetic protocol for the regioselective hydroxylation of sp(2) and sp(3) C–H bonds using a directing group, stoichiometric amounts of Cu and H(2)O(2). A wide array of aromatic ketones and aldehydes are oxidized in the carbonyl γ-position with remarkable yields. We also expanded this methodology to hydroxylate the β-position of alkylic ketones. Spectroscopic characterization, kinetics, and density functional theory calculations point toward the involvement of a mononuclear LCu(II)(OOH) species, which oxidizes the aromatic sp(2) C–H bonds via a concerted heterolytic O–O bond cleavage with concomitant electrophilic attack on the arene system. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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