Direct reversible decarboxylation from stable organic acids in dimethylformamide solution
Direct reversible decarboxylation from stable organic acids in dimethylformamide solution
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DOI：
10.1126/science.abb4129
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发表时间：
2020-07-31
期刊：
影响因子：
56.9
通讯作者：
Lundgren, Rylan J.
中科院分区：
文献类型：
--
作者：
Kong, Duanyang;Moon, Patrick J.;Lundgren, Rylan J.
有机化学中的许多经典和新兴方法依赖于二氧化碳（CO2）挤出来产生用于成键事件的反应性中间体。涉及微观逆反应-反应中间体的羧化-的合成反应通常使用非常不同的条件进行。我们报道了化学稳定的C（sp（3））羧酸酯，如芳基乙酸和丙二酸半酯，在二甲基甲酰胺溶液中进行非催化可逆脱羧反应。脱羧-羧化在其他条件相同的情况下，在对布朗斯台德酸的原脱羧具有抗性的底物中发生。同位素标记的羧酸可以通过简单地向极性非质子溶剂中的羧酸盐提供（CO 2）-C-13气氛而以高化学和同位素产率制备。对溶液中羧酸盐反应性的理解使得能够捕获醛、酮和α，β-不饱和酯的条件。
Many classical and emerging methodologies in organic chemistry rely on carbon dioxide (CO2) extrusion to generate reactive intermediates for bond-forming events. Synthetic reactions that involve the microscopic reverse-the carboxylation of reactive intermediates-have conventionally been undertaken using very different conditions. We report that chemically stable C(sp(3)) carboxylates, such as arylacetic acids and malonate half-esters, undergo uncatalyzed reversible decarboxylation in dimethylformamide solution. Decarboxylation-carboxylation occurs with substrates resistant to protodecarboxylation by Bronsted acids under otherwise identical conditions. Isotopically labeled carboxylic acids can be prepared in high chemical and isotopic yield by simply supplying an atmosphere of (CO2)-C-13 to carboxylate salts in polar aprotic solvents. An understanding of carboxylate reactivity in solution enables conditions for the trapping of aldehydes, ketones, and alpha,beta-unsaturated esters.