From Formamide to Purine: A Self-Catalyzed Reaction Pathway Provides a Feasible Mechanism for the Entire Process
文献类型：期刊论文
| 作者 | Wang, Jing1; Gu, Jiande1,2 ; Minh Tho Nguyen3; Springsteen, Greg4; Leszczynski, Jerzy1
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| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY B
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| 出版日期 | 2013-08-15 |
| 卷号 | 117期号:32页码:9333-9342 |
| ISSN号 | 1520-6106 |
| DOI | 10.1021/jp404540x |
| 文献子类 | Article |
| 英文摘要 | A formamide self-catalyzed mechanistic pathway that transforms formamide to purine through a five-membered ring intermediate has been explored by density functional theory calculations. The highlight of the mechanistic route detailed here is that the proposed pathway represents the simplest and lowest energy reaction pathway. All necessary reactants, including catalysts, are generated from a single initial compound, formamide. The most catalytically effective form of formamide is found to be the imidic acid isomer. The catalytic effect of formamide has been found to be much more significant than that of water. The self-catalytic mechanism revealed here provides a pathway with the lowest energy barriers among all reaction routes previously published. Several important reaction steps are involved in this mechanistic route: formylation-dehydration, Leuckart reduction, five- and six-member ring-closing, and deamination. Overall, a five-membered ring-closing is the rate-determining step in the present catalytic route, which is consistent with our previous mechanistic investigations. The activation energy of this rate-controlling step (ca. 27 kcal/mol) is significantly lower than the rate-determining step (ca. 34 kcal/mol) in the pathway from 4-aminoimidazole-5-carboxamidine described by Schleyer's group (Proc. Natl. Acad. Sci. U.S.A. 2007, 104, 17272-17277 ) and in the pyrimidine pathway (ca. 44 kcal/mol) reported by Sponer et al. (J. Phys. Chem. A 2012, 116, 720-726 ). The self-catalyzed mechanistic pathway reported herein is less energetically demanding than previously proposed routes. |
| WOS关键词 | PREBIOTIC SYNTHESIS ; AB-INITIO ; HYDROGEN-CYANIDE ; CONTINUUM MODEL ; RING FORMATION ; ADENINE ; ORIGIN ; DENSITY ; ACID ; LIFE |
| 资助项目 | NSF[00000000] ; NASA Astrobiology Program under the NSF Center for Chemical Evolution[CHE1004570] |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000323301000003 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://119.78.100.183/handle/2S10ELR8/277506]  |
| 专题 | 药物发现与设计中心 中科院受体结构与功能重点实验室 新药研究国家重点实验室 |
| 通讯作者 | Gu, Jiande |
| 作者单位 | 1.Jackson State Univ, Dept Chem, Interdisciplinary Nanotox Ctr, Jackson, MS 39217 USA; 2.Chinese Acad Sci, Shanghai Inst Mat Med, State Key Lab Drug Res, Drug Design & Discovery Ctr, Shanghai 201203, Peoples R China; 3.Univ Louvain, Dept Chem, B-3001 Louvain, Belgium; 4.Furman Univ, Dept Chem, Greenville, SC 29613 USA |
| 推荐引用方式 GB/T 7714 | Wang, Jing,Gu, Jiande,Minh Tho Nguyen,et al. From Formamide to Purine: A Self-Catalyzed Reaction Pathway Provides a Feasible Mechanism for the Entire Process[J]. JOURNAL OF PHYSICAL CHEMISTRY B,2013,117(32):9333-9342. |
| APA | Wang, Jing,Gu, Jiande,Minh Tho Nguyen,Springsteen, Greg,&Leszczynski, Jerzy.(2013).From Formamide to Purine: A Self-Catalyzed Reaction Pathway Provides a Feasible Mechanism for the Entire Process.JOURNAL OF PHYSICAL CHEMISTRY B,117(32),9333-9342. |
| MLA | Wang, Jing,et al."From Formamide to Purine: A Self-Catalyzed Reaction Pathway Provides a Feasible Mechanism for the Entire Process".JOURNAL OF PHYSICAL CHEMISTRY B 117.32(2013):9333-9342. |
入库方式： OAI收割
来源：上海药物研究所
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