DFT study on selective autocatalyzed alpha-alkylation of ketones with alcohols
文献类型：期刊论文
| 作者 | Yang, Xue2; Li, Da-Lei1 ; Zhang, Hai-Long1; Sun, Wang-Jie2; Zhao, Guo-Ming1,2
|
| 刊名 | JOURNAL OF CATALYSIS
 |
| 出版日期 | 2019-05-01 |
| 卷号 | 373页码:126-138 |
| 关键词 | DFT Selectivity Autocatalysis alpha-Alkylation of ketones TOF Base Mechanism |
| ISSN号 | 0021-9517 |
| DOI | 10.1016/j.jcat.2019.03.033 |
| 通讯作者 | Zhao, Guo-Ming(zhaoguoming1980@foxmail.com) |
| 英文摘要 | Base-promoted transition-metal-free alpha-alkylation of ketones with alcohols is an efficient, practical, and green method for the formation of new C-C bonds. Here, we present a OFT study on NaOH/KOH-promoted selective autocatalyzed alpha-alkylation of ketones with alcohols. For the production of alkylated alcohol, the disodium alkoxide species Na1D is the mediator, and the transformation involves four stages: (I) aldehyde formation; (II) aldol condensation; (III) chalcone reduction to generate an alkylated ketone and an aldehyde; and (IV) reduction of the alkylated ketone to produce an alkylated alcohol. Stage I only occurs at the beginning of the reaction, and the subsequent reaction proceeds via the catalytic cycle cyc-Na involving stages II, III, and IV. The energetic span and the turnover frequency (TOF) of cyc-Na are 35.2 kcal/mol and 5.7 x 10(-7) 1 /s, respectively. For the production of alkylated ketone, the dipotassium alkoxide species KID is the mediator, and the transformation includes dioxygen-assisted oxidation of alkylated alcohol (stage V) and the above four stages. Stage I only takes place initially, too, but the subsequent reaction has two selectable channels. The main channel is the catalytic cycle cyc-K consisting of stages II and III. The energetic span and the TOF of cyc-K are 29.5 kcal/mol and 8.8 x 10(-5) 1/s, respectively. The side channel involves stages II, III, IV, and V, in which the apparent activation energy (ME) is 34.1 kcal/mol. The calculations present the TOF-determining intermediates and the TOF-determining transition state, and uncover the essence of autocatalysis and the origins of the product selectivity. One important finding is the alkylated ketone selectivity may be enhanced by adding a small quantity of aldehyde corresponding to the alcohol reactant and lowering the reaction temperature. (C) 2019 Elsevier Inc. All rights reserved. |
| WOS关键词 | MEERWEIN-PONNDORF-VERLEY ; CATALYZED N-ALKYLATION ; HYBRID DENSITY FUNCTIONALS ; TRANSITION-METAL ; C-C ; BORROWING HYDROGEN ; ALLYLIC ALKYLATION ; BOND FORMATION ; MECHANISM ; REDUCTION |
| 资助项目 | 13th Five-year Science and Technology Project of Jilin Provincial Education Department[JJKH20170215KJ] ; Project of the 13th Five-year General Plan of Jilin Provincial Education Science[GH180442] |
| WOS研究方向 | Chemistry ; Engineering |
| 语种 | 英语 |
| WOS记录号 | WOS:000474321300013 |
| 出版者 | ACADEMIC PRESS INC ELSEVIER SCIENCE |
| 资助机构 | 13th Five-year Science and Technology Project of Jilin Provincial Education Department ; Project of the 13th Five-year General Plan of Jilin Provincial Education Science |
| 源URL | [http://ir.xao.ac.cn/handle/45760611-7/2890]  |
| 专题 | 恒星形成与演化研究团组 新疆天文台_计算机技术室 |
| 通讯作者 | Zhao, Guo-Ming |
| 作者单位 | 1.Chinese Acad Sci, Xinjiang Astron Observ, Urumqi 830011, Peoples R China 2.Jilin Inst Chem Technol, Sch Sci, Jilin 132022, Jilin, Peoples R China |
| 推荐引用方式 GB/T 7714 | Yang, Xue,Li, Da-Lei,Zhang, Hai-Long,et al. DFT study on selective autocatalyzed alpha-alkylation of ketones with alcohols[J]. JOURNAL OF CATALYSIS,2019,373:126-138. |
| APA | Yang, Xue,Li, Da-Lei,Zhang, Hai-Long,Sun, Wang-Jie,&Zhao, Guo-Ming.(2019).DFT study on selective autocatalyzed alpha-alkylation of ketones with alcohols.JOURNAL OF CATALYSIS,373,126-138. |
| MLA | Yang, Xue,et al."DFT study on selective autocatalyzed alpha-alkylation of ketones with alcohols".JOURNAL OF CATALYSIS 373(2019):126-138. |
入库方式： OAI收割
来源：新疆天文台
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。