Renewable Solvents for Palladium-Catalyzed Carbonylation Reactions

Abstract

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.

Replacement of Less-Preferred Dipolar Aprotic and Ethereal Solvents in Synthetic Organic Chemistry with More Sustainable Alternatives

“…It was found that aminocarbonylation proceeded well in DMC while alkoxycarbonylation was successfully conducted in DMC and 2-MeTHF. 333 …”

An Expedient Approach to Pyrazolo[3,4-b]pyridine-3-carboxamides via Palladium-Catalyzed Aminocarbonylation

“…Numerous reports 23,33,46,47 outlining the aminocarbonylation of aryl (psuedo)halides typically describe the use of between 1 to 3 equivalents of CO surrogate. To determine if the transformation of 15 to carboxamide 16 could be achieved with less than 10 equivalents of CO, our attention turned to reducing the number of equivalents of our chosen CO surrogate (formic acid, mesyl chloride, and triethylamine) 33 with respect to aryl iodide 15 (Table 3), while keeping all other variables constant including the COware ® apparatus volume (20 mL).…”

Progress in the Synthesis of Aroyl Compounds

“…8). 2020 年, Bayer 等 [31] 报道了一种绿色、环保的合成 二芳基甲酮类化合物的方法. 他们以溴代芳烃和芳基硼 酸类化合物为原料, 乙酰丙酮钯为催化剂, 二(1-金刚烷 基)-正丁基膦氢碘化物(CataXCium AHI)为配体, 氢氧 化钠为碱, 9-甲基-9H-芴-9-羰基氯(COgen)为羰基源, 在 柠檬烯中反应 18 h 左右可制得二芳基甲酮类化合物, 收 率达 96%, 该反应底物适用性广泛, 同时适用于芳甲酰 胺、芳酸酯类化合物的合成.…”