Technical Name High Efficiency on Fixation of CO2 and Synthesis of Carboxylic acids and Epoxy Derivatives via Transition-Metal Catalysis
Project Operator National Tsing Hua University
Summary
Iron- and nickel-catalyzed synthesis of vinylic acids and acrylic acids from alkynes, Grignard reagents and fixation of CO2 was developed. This methodology features good to excellent yield, high regioselectivity, and broad functional group tolerance.
Synthesis of Bisphenol A diglycidyl ether (BADGE) via epoxidation with tungsten catalyst and hydrogen peroxide was demonstrated. The green process produces water as the by-product, which is the main feature of this synthetic methodology.
Scientific Breakthrough
1. An iron-catalyzed hygromagnesiation of alkynes with Grignard reagents and fixation of CO2 for the synthesis of vinylic acids was demonstrated. This methodology features good to excellent yield, high regioselectivity, and broad functional group tolerance. On the basis of literature report, the products diarylvinylic acids are bioactive. One of anticancer drugs, HIF-1, can also be synthesized through this methodology efficiently.

2. A nickel-catalyzed synthesis of trisubstituted acrylic acids from alkynes, Grignard reagents, and CO2 was developed. The reaction proceeds under ambient pressure of carbon dioxide with mild reaction conditions in short time. Totally 26 different alkynes were transformed into the corresponding acid products in good yields with high stereoselectivity. The synthetic method was successfully applied to a gram-scale synthesis of product.

3. Synthesis of Bisphenol A diglycidyl ether (BADGE) via epoxidation with tungsten catalyst and hydrogen peroxide was demonstrated. The green process produces water as the by-product, which is the main feature of this synthetic methodology. Highly activated tungsten catalyst [Aliquat336]3{PO4[W(O2)2O]4} works well in the reaction and get the epoxidation product BADGE up to 91%. This methodology can further be applied in polymer synthesis.
Industrial Applicability
材料科技、環境化學。1.提供2種反應條件溫和之金屬催化合成多取代丙烯酸化合物之方法,產物可進一步應用於藥物之研發與高分子之合成。
2.提供低汙染之鎢金屬催化進行環氧化反應之方法,可進一部應用於特用化學品之製程改良。
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