Solvents constitute the largest component for many chemical processes and substitution of nonrenewable solvents is a longstanding goal for green chemistry. Here, we show that Pd-catalyzed carbonylative couplings, such as carbonylative cross-couplings, aminocarbonylations, and alkoxycarbonylations, can be successfully realized using renewable solvents. The present research covers not only well-established renewable solvents, such as 2-methyltetrahydrofuran (2MeTHF), limonene, and dimethyl carbonate, but also recently introduced biomass-derived 1,1-diethoxyethane, isosorbide dimethyl ether, eucalyptol, rose oxide, γ-terpinene, and α-pinene. The carbonylative coupling of boronic acids and aryl bromides works well in limonene. Aminocarbonylation gave excellent results in dimethyl carbonate, α-pinene, and limonene, while alkoxycarbonylation was successful in 2MeTHF, α-pinene, γ-terpinene, and dimethyl carbonate. The developed methods based on renewable solvents can be used for the synthesis of commercial drug Trimetozine and an analogue of Itopride.

中文翻译：

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钯催化羰基化反应的可再生溶剂

溶剂是许多化学过程的最大组成部分，不可再生溶剂的替代是绿色化学的长期目标。在这里，我们表明使用可再生溶剂可以成功实现Pd催化的羰基偶联，例如羰基交叉偶联，氨基羰基化和烷氧羰基化。本研究不仅涵盖成熟的可再生溶剂，例如2-甲基四氢呋喃（2MeTHF），柠檬烯和碳酸二甲酯，而且最近还引入了生物质衍生的1,1-二乙氧基乙烷，异山梨醇二甲醚，桉树油，氧化玫瑰，γ -松油烯和α-松油。硼酸和芳基溴化物的羰基化偶联在柠檬烯中效果很好。氨基羰基化在碳酸二甲酯，α-pine烯和li烯中获得了优异的结果，而在2MeTHF，α-pine烯，γ-萜品烯和碳酸二甲酯中烷氧基羰基化成功。基于可再生溶剂的已开发方法可用于合成商业药物Trimetozine和Itopride的类似物。