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Article Abstract
A (XantPhos)Pd-catalyzed decarbonylative C-H functionalization of azoles with difluoromethyl anhydrides is reported. Under the optimized conditions, azole substrates react selectively at the C(2)-position to afford CFH-substituted benzoxazole, oxazole, benzothiazole, thiazole, and benzimidazole products. Organometallic mechanistic studies reveal that XantPhos enforces an unusual seesaw geometry of the key Pd(CFH)(carboxylate) intermediate, which may be responsible for the effectiveness of this ligand.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC12402946 | PMC |
| http://dx.doi.org/10.1021/acs.orglett.5c02175 | DOI Listing |
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A (XantPhos)Pd-catalyzed decarbonylative C-H functionalization of azoles with difluoromethyl anhydrides is reported. Under the optimized conditions, azole substrates react selectively at the C(2)-position to afford CFH-substituted benzoxazole, oxazole, benzothiazole, thiazole, and benzimidazole products. Organometallic mechanistic studies reveal that XantPhos enforces an unusual seesaw geometry of the key Pd(CFH)(carboxylate) intermediate, which may be responsible for the effectiveness of this ligand.
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Article Synopsis
- The manuscript presents a novel palladium-catalyzed cyclization method using carboxylic acids and terminal alkynes, which showcases its potential for creating complex organic molecules.
- This technique is significant as it allows carboxylic acids, traditionally underutilized, to serve as effective building blocks in intramolecular cycloaddition and addresses long-standing challenges in synthesizing substituted naphthalenes.
- The reaction demonstrates a wide range of substrate compatibility and functional group tolerance, making it applicable for scalable synthesis in organic chemistry, drug discovery, and material science.