Linfeng Zhang,Changpo Ma,Chenyu Wang,Guangyu Sun,Yongqi Shu,Wenya Zou,Tao Yang,Weiran Yang
Glyceric acid (GA), a glycerol derivative, can be used as a versatile platform molecule to produce value-added chemicals. Succinic acid (SA) is a very important bio-based molecule that acts as a fine chemical and is used in biodegradable polymer synthesis. It has been shown earlier that GA can be effectively converted to the platform chemical 3-iodopropionic acid (3-IPA) with a RhCl3/HI catalyst system. In this work, we first explored the production of SA from 3-IPA by carbonylation. With RhCl3 as the catalyst and acetic acid (AA) and water as the solvent, as high as 78% yield of SA can be achieved. Considering the similarity of the catalysts used in two steps, we then further probed the one-step synthesis of SA directly from GA. Under optimized reaction conditions, 71% yield of SA can be obtained directly from GA by reductive carbonylation with RhCl3 and I2 as the catalyst under H2 and CO atmospheres. This is the first report of the direct conversion of GA to SA, which provides a novel method for glycerol valorization.
Changpo Ma,Ying Lai,Tiange Zhao,Xiaoxuan Zhang,Haichao Liu,Weiran Yang
α,ω-Dicarboxylic acids are important intermediates for the preparation of polyamides , polyesters and polyurethanes . However, their production pathways are limited and usually suffer from low efficiency and environmental problems. Here, we report an innovative approach to synthesize C+2 dicarboxylic acids directly from cyclic ethers by dicarbonylation. Different from the general findings that C+1 monocarboxylic acids are produced by carbonylation of cyclic ethers involving alkene intermediates, in this work, by manipulating the reaction system with RhCl 3 and iodine in acetic acid, diiodide-substituted intermediates were selectively formed and subsequently converted to dicarboxylic acids in the presence of H 2 and CO. As high as 84% yield of adipic acid was obtained directly from tetrahydrofuran. This catalytic system is applicable not only to a wide variety of cyclic ethers but also to different primary diols to synthesize C2-elongated α,ω-dicarboxylic acids. This work provides a novel dicarbonylation strategy for the efficient synthesis of adipic acid, glutaric acid and other important α,ω-dicarboxylic acids (such as 1,7-heptanedioic acid and 1,8-octanedioic acid) that are still not easily synthesized by other methods.
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