Zhao, Fei;
Zhou, Zhi;
Lu, Yangbin;
Qiao, Jin;
Zhang, Xiaoning;
Gong, Xin;
Liu, Siyu;
... Yi, Wei; + view all
(2021)
Chemo-, Regio-, and Stereoselective Assembly of Polysubstituted Furan-2(5H)-ones Enabled by Rh(III)-Catalyzed Domino C–H Alkenylation/Directing Group Migration/Lactonization: A Combined Experimental and Computational Study.
ACS Catalysis
, 11
(22)
pp. 13921-13934.
10.1021/acscatal.1c03846.
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Abstract
Exploring multistep cascade reactions triggered by C–H activation are recognized as appealing, yet challenging. Herein, we disclose a Rh(III)-catalyzed domino C–H coupling of N-carbamoyl indoles and 4-hydroxy-2-alkynoates for the streamlined assembly of highly functionalized furan-2(5H)-ones in which the carbamoyl-directing group (DG) is given a dual role of an auxiliary group and a migrating acylating reagent via the cleavage of stable C–N bonds at room temperature. More importantly, the obtained furan-2(5H)-one skeleton could be further functionalized under air in situ via C5–H hydroxylation by simply switching the solvent or additive, providing fully substituted furan-2(5H)-ones with the installation of an alcohol-based C5 quaternary carbon center. Detailed experimental studies and density functional theory calculations reveal that a Rh(III)-mediated tandem C–H activation/alkyne insertion/DG migration/lactonization accounts for the developed transformation to achieve high functionalities with the observed exclusive selectivity. The potential biological application of the obtained furan-2(5H)-ones as a class of potent PPARγ ligands further highlights the synthetic utility of the developed methodology. This protocol is endowed with several salient features including efficient multistep cascade triggered by C–H activation, excellent chemo-, regio-, and stereoselectivity, high bond-forming efficiency (e.g., two C–C and two C–O bonds), solvent- or additive-controlled product selectivity, good functional-group compatibility, and mild redox-neutral conditions.
| Type: | Article |
|---|---|
| Title: | Chemo-, Regio-, and Stereoselective Assembly of Polysubstituted Furan-2(5H)-ones Enabled by Rh(III)-Catalyzed Domino C–H Alkenylation/Directing Group Migration/Lactonization: A Combined Experimental and Computational Study |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/acscatal.1c03846 |
| Publisher version: | https://doi.org/10.1021/acscatal.1c03846 |
| Language: | English |
| Additional information: | This version is the author-accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. |
| Keywords: | rhodium(III) catalysis, C−H activation, domino reaction, furan-2(5H)-ones, 5-hydroxyfuran-2(5H)-ones, DFT calculations. |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10167666 |
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