钯催化的唑类化合物的脱羰C-H二氟甲基化反应
Palladium-Catalyzed Decarbonylative C-H Difluoromethylation of Azoles.
作者信息
Gu Frances, Lalloo Naish, Wearing Emily R, Sanford Melanie S
机构信息
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States.
出版信息
Org Lett. 2025 Aug 1;27(30):8144-8148. doi: 10.1021/acs.orglett.5c02175. Epub 2025 Jul 22.
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.
摘要
报道了一种（XantPhos）钯催化的唑类与二氟甲基酸酐的脱羰C-H官能化反应。在优化条件下，唑类底物在C（2）位选择性反应，得到CFH取代的苯并恶唑、恶唑、苯并噻唑、噻唑和苯并咪唑产物。有机金属机理研究表明，XantPhos使关键的Pd（CFH）（羧酸盐）中间体具有不寻常的跷跷板几何形状，这可能是该配体有效性的原因。
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