CO _2 on a tightrope: Stabilization, room-temperature decarboxylation, and sodium-induced carboxylate migration

H?u?ermann A.; Rominger F.; Straub B.F.

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CO _2 on a tightrope: Stabilization, room-temperature decarboxylation, and sodium-induced carboxylate migration

机译：钢丝上的CO _2：稳定性，室温脱羧和钠诱导的羧酸盐迁移

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A sterically shielded 3-substituted zwitterionic N,N- dimethylisotryptammonium carboxylate has been synthesized by consecutive chemoselective double alkylation of indole. The carboxylate undergoes a quantitative and unusually facile decarboxylation in dimethyl sulfoxide (DMSO) or dimethyl formamide (DMF) at room temperature. The breaking of a nearly equidistant hydrogen bond by solvent molecules initiates heterolytic C-C cleavage. The decarboxylation rate decreases with increasing CO _2 partial pressure, proving the competitiveness of protonation and re-carboxylation of the carbanionic intermediate. Corresponding spiro compounds containing silylene and stannylene moieties show high thermal stability. Addition of an excess of methyllithium to the sodium salt triggers a reaction sequence comprising a deprotonation, carboxylate transfer, and nucleophilic trapping of the rearranged carboxylate by another equivalent of methyllithium. Hydrolytic work-up of the geminal diolate leads to an acetyl product. The role of the sodium counterion and the mechanism of the rearrangement have been unraveled by deuteration experiments.

机译：通过吲哚的连续化学选择性双烷基化反应合成了空间屏蔽的3-取代的两性离子的N，N-二甲基异胰二铵羧酸盐。在室温下，羧酸盐在二甲基亚砜（DMSO）或二甲基甲酰胺（DMF）中进行定量且异常容易的脱羧。溶剂分子破坏几乎等距的氢键会引发杂化C-C裂解。脱羧速率随CO _2分压的增加而降低，证明了碳负离子中间体的质子化和再羧化的竞争力。相应的含有亚甲硅烷基和亚锡亚烷基部分的螺环化合物显示出高的热稳定性。向钠盐中添加过量的甲基锂会触发反应序列，该反应序列包括去质子化，羧酸盐转移以及另一等量的甲基锂对重排的羧酸盐的亲核捕获。双羟甲基双羟乙酸酯的水解后处理得到乙酰基产物。氘代实验尚未阐明钠抗衡离子的作用和重排的机理。

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《Chemistry: A European journal》 |2012年第44期|共12页
作者
H?u?ermann A.; Rominger F.; Straub B.F.;
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正文语种 eng
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carbon dioxide; decarboxylation; rearrangement; spiro compounds; zwitterions;

机译：二氧化碳;脱羧;重排;螺环化合物;两性离子;

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1. CO _2 on a tightrope: Stabilization, room-temperature decarboxylation, and sodium-induced carboxylate migration [J] . H?u?ermann A., Rominger F., Straub B.F. Chemistry: A European journal . 2012,第44期

机译：钢丝上的CO _2：稳定性，室温脱羧和钠诱导的羧酸盐迁移
2. Role of the Carboxylate in Enzyme-Catalyzed Decarboxylation of Orotidine 5'-Monophosphate: Transition State Stabilization Dominates Over Ground State Destabilization [J] . Goryanova Bogdana, Amyes Tina L., Richard John P. Journal of the American Chemical Society . 2019,第34期

机译：羧酸盐在Orotidine 5'-单磷酸盐的酶催化脱羧中的作用：过渡态稳定比基态稳定更重要
3. Room-Temperature Micron-Scale Exciton Migration in a Stabilized Emissive Molecular Aggregate [J] . Caram Justin R., Doria Sandra, Eisele Dorthe M., Nano letters . 2016,第11期

机译：在稳定的发射分子聚集体中的室温微米级激子迁移。
4. Electrochemical Studies of Imidazolium Carboxylate Adducts in a Room-Temperature Ionic Liquid [C] . G. T. Cheek, D. F. Roeper, W. Pearson, Molten salts and ionic liquids 19 . 2014

机译：室温离子液体中咪唑鎓羧酸盐加合物的电化学研究
5. I. Multicatalysis: Development of a Bismuth(III) triflate-catalyzed Nucleophilic addition/ Hydrofunctionalization Reaction in the Synthesis of Complex Heterocycles II. C--H Arylation of Arenes and Heteroarenes with Palladium-Carboxylate Catalysts: Identification of the Catalyst Resting State and the Crucial Role of Pivalate Ligand in Stabilization of the Catalyst III. C--H Arylation of Heteroarenes with Palladium-Carboxylate Catalysts: Importance of Phosphine Ligand for Basic Heteroarene Substrates IV. C--H Arylation of Heteroarenes with Palladium-Carboxylate Catalysts: Effect of the Properties of Basic Heteroarene Substrates on Direct Arylations. [D] . Tundel, Rachel E. 2011

机译：I.多催化作用：在复杂的杂环化合物的合成中三氟甲磺酸铋（III）催化的亲核加成/加氢官能化反应的发展。羰基钯催化剂对芳烃和杂芳烃的CH-H芳基化反应：催化剂静止状态的鉴定以及新戊酸酯配体在稳定催化剂中的关键作用III。羰基钯催化剂催化杂芳烃的CH芳基化：膦配体对基础杂芳烃基质的重要性IV。杂芳烃与钯-羧酸酯的CH芳基化：碱性杂芳烃底物性能对直接芳基化的影响。
6. Facile room-temperature synthesis of carboxylated graphene oxide-copper sulfide nanocomposite with high photodegradation and disinfection activities under solar light irradiation [O] . Shuyan Yu, Jincheng Liu, Wenyu Zhu, -1

机译：在日光照射下易于室温合成具有高光降解和杀菌活性的羧化氧化石墨烯-硫化铜纳米复合材料
7. Role of the Carboxylate in Enzyme-Catalyzed Decarboxylation of Orotidine 5′-Monophosphate: Transition State Stabilization Dominates Over Ground State Destabilization [O] . Bogdana Goryanova, Tina L. Amyes, John P. Richard 2019

机译：羧酸羧酸盐的作用催化羧酸丁酯5'-单磷酸酯：过渡状态稳定化在地面稳定下占据稳定性

CO _2 on a tightrope: Stabilization, room-temperature decarboxylation, and sodium-induced carboxylate migration

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