pH-controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways
文献类型：期刊论文
| 作者 | Butch, Christopher J.5,6,8; Wang, Jing9; Gu, Jiande1 ; Vindas, Rebeca3; Crowe, Jacob7,8; Pollet, Pamela4; Gelbaum, Leslie4; Leszczynski, Jerzy9; Krishnamurthy, Ramanarayanan2; Liotta, Charles L.4,8
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| 刊名 | JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
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| 出版日期 | 2016-07 |
| 卷号 | 29期号:7页码:352-360 |
| 关键词 | Dihydroxyfumaric acid Glyoxylic acid pH control Formaldehyde |
| ISSN号 | 0894-3230 |
| DOI | 10.1002/poc.3542 |
| 文献子类 | Article |
| 英文摘要 | The reactions of dihydroxyfumarate with glyoxylate and formaldehyde exhibit a unique pH-controlled mechanistic divergence leading to different product suites by two distinct pathways. The divergent reactions proceed via a central intermediate (2,3-dihydroxy-oxalosuccinate, 3, in the reaction with glyoxylate and 2-hydroxy-2-hydroxymethyl-3-oxosuccinate, 14, in the reaction with formaldehyde). At pH 7-8, products (7, 8, and 15) exclusively from a decarboxylation of the intermediate are observed, while at pH 13-14, products (9, 10, and 16) solely derived from a hydroxide-promoted fragmentation of the intermediate are formed. The decarboxylative and fragmentation pathways are mutually exclusive and do not appear to coexist under the range of pH (7-14) conditions investigated. Herein, we employ a combination of quantitative C-13 NMR measurements and density functional theory calculations to provide a rationale for this pH-driven reaction divergence. These rationalizations also hold true for the reactions of dihydroxyfumarate produced in situ by the catalytic cyanide-mediated dimerization of glyoxylate. In addition, the non-enzymatic decarboxylation and fragmentation transformations of these central intermediates (3 and 14) appear to have intriguing parallels to the enzymatic reactions of oxalosuccinate and formation of glyceric acid derivatives in extant metabolism - the high and low pH mimicking the precise control exerted by the enzymes over reaction pathways. Copyright (C) 2016 John Wiley & Sons, Ltd. |
| WOS关键词 | DENSITY FUNCTIONALS ; CARBON-DIOXIDE ; ACID ; CHEMISTRY ; KINETICS ; OXALATE ; ACETATE |
| 资助项目 | NSF[00000000] ; NASA Astrobiology program under the National Science Foundation (NSF) Center for Chemical Evolution[CHE-1004570] |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000380042000004 |
| 出版者 | WILEY |
| 源URL | [http://119.78.100.183/handle/2S10ELR8/275968]  |
| 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 | Krishnamurthy, Ramanarayanan; Liotta, Charles L. |
| 作者单位 | 1.Chinese Acad Sci, Shanghai Inst Mat Med, State Key Lab Drug Res, Drug Design & Discovery Ctr, Shanghai 201203, Peoples R China; 2.Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA; 3.Georgia State Univ, Dept Chem, Atlanta, GA 30302 USA 4.Georgia Inst Technol, Sch Chem & Biochem, Atlanta, GA 30332 USA; 5.Emory Univ, Dept Chem, Atlanta, GA 30322 USA; 6.Tokyo Inst Technol, Earth Life Sci Inst, Atlanta, GA 30322 USA; 7.Michigan State Univ, Dept Chem Engn & Mat Sci, E Lansing, MI 48824 USA; 8.Georgia Inst Technol, Sch Chem & Biol Engn, Atlanta, GA 30332 USA; 9.Jackson State Univ, Dept Chem & Biochem, Jackson, MS 39217 USA; |
| 推荐引用方式 GB/T 7714 | Butch, Christopher J.,Wang, Jing,Gu, Jiande,et al. pH-controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways[J]. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY,2016,29(7):352-360. |
| APA | Butch, Christopher J..,Wang, Jing.,Gu, Jiande.,Vindas, Rebeca.,Crowe, Jacob.,...&Liotta, Charles L..(2016).pH-controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways.JOURNAL OF PHYSICAL ORGANIC CHEMISTRY,29(7),352-360. |
| MLA | Butch, Christopher J.,et al."pH-controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways".JOURNAL OF PHYSICAL ORGANIC CHEMISTRY 29.7(2016):352-360. |
入库方式： OAI收割
来源：上海药物研究所
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