| Base-Induced Mechanistic Variation in Palladium-Catalyzed Carbonylation of Aryl Iodides | |
| Department | 羰基合成与选择氧化国家重点实验室 |
| Hu YH(胡严鹤); Liu J(刘婧); Lv ZX(吕志新); Luo XC(罗贤才); Zhang H(张恒); Lan Y(蓝宇); Lei AW(雷爱文) | |
| 2010 | |
| Source Publication | J. Am. Chem. Soc.
 |
| ISSN | 0002-7863 |
| Volume | 132Pages:3153-3158 |
| Abstract | A mechanism, which is distinct from the traditional one when sodium alkoxide was used instead of tertiary amines, was proposed for the alkoxycarbonylation of aryl iodides. The catalytic cycle was composed of oxidative addition, subsequent ArPdOR formation, CO insertion to Pd-OR, and final reductive elimination of ArPdCOOR. The kinetic simultaneity of the formation of deiodinated side product from the aryl iodide and aldehyde from corresponding alcohol provided strong evidence for the existence of ArPdOR species. The observation of thioether, as the other competitive product in palladium catalyzed thiocarbonylation of aryl iodides and sodium alkylthiolate, also indicate the possibility of metathesis between ArPdI and sodium alkylthiolate. Preliminary kinetic studies revealed that neither oxidative addition nor reductive elimination was rate limiting. DFT calculation displayed preference for CO insertion into Pd-OR bond. The advantage of this novel mechanism had been demonstrated in the facile alkoxycarbonylation and thiocarbonylation. The ethoxycarbonylation of aryl iodides under room temperature and balloon pressure of CO in the presence of EtONa were examined, and good to high yields were obtained; the t-butoxycarbonylation reactions in the presence of t-BuONa were achieved, and the alkylthiocarbonylation (including the t-butylthiocarbonylation) of aryl iodides in the presence of sodium alkylthiolate were also investigated. |
| Subject Area | 物理化学 |
| Funding Organization | National Natural Science Foundation of China (20772093;20832003) |
| Indexed By | SCI |
| Language | 英语 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.licp.cn/handle/362003/417 |
| Collection | 羰基合成与选择氧化国家重点实验室（OSSO） |
| Corresponding Author | Lei AW(雷爱文) |
| Recommended Citation GB/T 7714 | Hu YH,Liu J,Lv ZX,et al. Base-Induced Mechanistic Variation in Palladium-Catalyzed Carbonylation of Aryl Iodides[J]. J. Am. Chem. Soc.,2010,132:3153-3158. |
| APA | 胡严鹤.,刘婧.,吕志新.,罗贤才.,张恒.,...&雷爱文.(2010).Base-Induced Mechanistic Variation in Palladium-Catalyzed Carbonylation of Aryl Iodides.J. Am. Chem. Soc.,132,3153-3158. |
| MLA | 胡严鹤,et al."Base-Induced Mechanistic Variation in Palladium-Catalyzed Carbonylation of Aryl Iodides".J. Am. Chem. Soc. 132(2010):3153-3158. |
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