A DFT Study on the Conversion of Aryl Iodides to Alkyl Iodides: Reductive Elimination of R-I from Alkylpalladium Iodide Complexes with Accessible -Hydrogens
文献类型：期刊论文
| 作者 | Hao, Wei1; Wei, Junnian1; Chi, Yue1; Walsh, Patrick J.2; Xi, Zhenfeng1 |
| 刊名 | CHEMISTRY-A EUROPEAN JOURNAL
 |
| 出版日期 | 2016-03-01 |
| 卷号 | 22期号:10页码:3422-3429 |
| 关键词 | Alkylpalladium Iodide Complexes Computational Chemistry Reaction Mechanisms Reductive Elimination Synthetic Methods |
| ISSN号 | 0947-6539 |
| DOI | 10.1002/chem.201503910 |
| 文献子类 | Article |
| 英文摘要 | DFT calculations have been performed on the palladium-catalyzed carboiodination reaction. The reaction involves oxidative addition, alkyne insertion, C-N bond cleavage, and reductive elimination. For the alkylpalladium iodide intermediate, LiOtBu stabilizes the intermediate in non-polar solvents, thus promoting reductive elimination and preventing -hydride elimination. The C-N bond cleavage process was explored and the computations show that PPh3 is not bound to the Pd center during this step. Experimentally, it was demonstrated that LiOtBu is not necessary for the oxidative addition, alkyne insertion, or C-N bond cleavage steps, lending support to the conclusions from the DFT calculations. The turnover-limiting steps were found to be C-N bond cleavage and reductive elimination, whereas oxidative addition, alkyne insertion, and formation of the indole ring provide the driving force for the reaction. |
| WOS关键词 | CROSS-COUPLING REACTIONS ; PALLADIUM-CATALYZED BROMOALKYNYLATION ; ARYLPALLADIUM(II) HALIDE-COMPLEXES ; REVERSIBLE OXIDATIVE ADDITION ; BIDENTATE NITROGEN LIGANDS ; BOND FORMATION ; MECHANISTIC INSIGHT ; EFFICIENT SYNTHESIS ; EXCHANGE-REACTIONS ; PD(III) COMPLEXES |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000371419200034 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/171028]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 通讯作者 | Xi, Zhenfeng |
| 作者单位 | 1.Peking Univ, Coll Chem, Key Lab Bioorgan Chem & Mol Engn, BNLMS,Minist Educ, Beijing 100871, Peoples R China 2.Univ Penn, Dept Chem, Roy & Diana Vagelos Labs, 231 South 34th St, Philadelphia, PA 19104 USA |
| 推荐引用方式 GB/T 7714 | Hao, Wei,Wei, Junnian,Chi, Yue,et al. A DFT Study on the Conversion of Aryl Iodides to Alkyl Iodides: Reductive Elimination of R-I from Alkylpalladium Iodide Complexes with Accessible -Hydrogens[J]. CHEMISTRY-A EUROPEAN JOURNAL,2016,22(10):3422-3429. |
| APA | Hao, Wei,Wei, Junnian,Chi, Yue,Walsh, Patrick J.,&Xi, Zhenfeng.(2016).A DFT Study on the Conversion of Aryl Iodides to Alkyl Iodides: Reductive Elimination of R-I from Alkylpalladium Iodide Complexes with Accessible -Hydrogens.CHEMISTRY-A EUROPEAN JOURNAL,22(10),3422-3429. |
| MLA | Hao, Wei,et al."A DFT Study on the Conversion of Aryl Iodides to Alkyl Iodides: Reductive Elimination of R-I from Alkylpalladium Iodide Complexes with Accessible -Hydrogens".CHEMISTRY-A EUROPEAN JOURNAL 22.10(2016):3422-3429. |
入库方式： OAI收割
来源：大连化学物理研究所
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