Palladium-Based Dyotropic Rearrangement Enables A Triple Functionalization of Gem-Disubstituted Alkenes: An Unusual Fluorolactonization Reaction

被引:27
作者
Feng, Qiang [1 ]
Liu, Chen-Xu [1 ]
Wang, Qian [1 ]
Zhu, Jieping [1 ]
机构
[1] Ecole Polytech Fed Lausanne, Inst Chem Sci & Engn, Lab Synth & Nat Prod LSPN, EPFL,SB,ISIC,LSPN, BCH 304, CH-1015 Lausanne, Switzerland
关键词
1-Fluoroalkylcarboxylate; Dyotropic Rearrangement; Fluorination; Fluorolactonization; High Valent Palladium; SYMMETRY CONTROLLED REACTIONS; C-H FLUORINATION; CARBOXYLIC-ACIDS; DIACETOXYLATION; LACTONIZATION; DIFLUORINATION; DERIVATIVES;
D O I
10.1002/anie.202316393
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report in this paper a Pd(II)-catalyzed migratory gem-fluorolactonization of ene-carboxylic acids. Reaction of 4-methylenealkanoic acid derivatives with Selectfluor in the presence of Pd(OAc)(2) (1.0 mol %) at room temperature affords fluorolactones in good to excellent yields. 2-(2-Methylenecycloalkanyl)acetic acids are transformed to bridged fluorolactones under identical conditions. One C-C, one C-O and one tertiary C-F bond were generated along the gem-disubstituted carbon-carbon double bond in this operationally simple transformation. Trapping experiments indicates that the reaction is initiated by a 5-exo-trig oxypalladation followed by Pd oxidation, regioselective ring-enlarging 1,2-alkyl/Pd(IV) dyotropic rearrangement and C-F bond forming reductive elimination cascade. Post-transformations of these fluorolactones taking advantage of the electrophilicity of the 1-fluoroalkylcarboxylate function are also documented.
引用
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页数:5
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