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| DFT study on selective autocatalyzed alpha-alkylation of ketones with alcohols | |
Zhao, Guo-Ming1,2; Sun, Wang-Jie1; Zhang, Hai-Long2 ; Li, Da-Lei2; Yang, Xue1
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| 2019-05-01 | |
| Source Publication | JOURNAL OF CATALYSIS
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| ISSN | 0021-9517 |
| Volume | 373Pages:126-138 |
| Contribution Rank | 2 |
| Abstract | 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. |
| Keyword | DFT Selectivity Autocatalysis alpha-Alkylation of ketones TOF Base Mechanism |
| DOI | 10.1016/j.jcat.2019.03.033 |
| Indexed By | SCI |
| Language | 英语 |
| WOS Keyword | MEERWEIN-PONNDORF-VERLEY ; CATALYZED N-ALKYLATION ; HYBRID DENSITY FUNCTIONALS ; TRANSITION-METAL ; C-C ; BORROWING HYDROGEN ; ALLYLIC ALKYLATION ; BOND FORMATION ; MECHANISM ; REDUCTION |
| Funding Project | 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 Research Area | Chemistry ; Engineering |
| WOS Subject | Chemistry, Physical ; Engineering, Chemical |
| WOS ID | WOS:000474321300013 |
| Publisher | ACADEMIC PRESS INC ELSEVIER SCIENCE |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.xao.ac.cn/handle/45760611-7/2891 |
| Collection | 射电天文研究室_恒星形成与演化研究团组 计算机技术应用研究室 |
| Corresponding Author | Zhao, Guo-Ming |
| Affiliation | 1.Jilin Inst Chem Technol, Sch Sci, Jilin 132022, Jilin, Peoples R China 2.Chinese Acad Sci, Xinjiang Astron Observ, Urumqi 830011, Peoples R China |
| First Author Affilication | Xinjiang Astronomical Observatory, Chinese Academy of Sciences |
| Corresponding Author Affilication | Xinjiang Astronomical Observatory, Chinese Academy of Sciences |
| Recommended Citation GB/T 7714 | Zhao, Guo-Ming,Sun, Wang-Jie,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 | Zhao, Guo-Ming,Sun, Wang-Jie,Zhang, Hai-Long,Li, Da-Lei,&Yang, Xue.(2019).DFT study on selective autocatalyzed alpha-alkylation of ketones with alcohols.JOURNAL OF CATALYSIS,373,126-138. |
| MLA | Zhao, Guo-Ming,et al."DFT study on selective autocatalyzed alpha-alkylation of ketones with alcohols".JOURNAL OF CATALYSIS 373(2019):126-138. |
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| Zhao-2019-DFT study （3009KB） | 期刊论文 | 出版稿 | 开放获取 | CC BY-NC-SA | View Application Full Text | |
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