Rh(i)-催化的对映选择性和可规模化的 1,3-二烯与二烷基丙炔二羧酸酯的[4 + 2]环加成反应。
Rh(i)-Catalyzed enantioselective and scalable [4 + 2] cycloaddition of 1,3-dienes with dialkyl acetylenedicarboxylates.
机构信息
School of Science, Harbin Institute of Technology, Shenzhen, 518055, China.
出版信息
Org Biomol Chem. 2020 Apr 15;18(15):2956-2961. doi: 10.1039/d0ob00361a.
An asymmetric intermolecular [4 + 2] cycloaddition of 1,3-dienes with dialkyl acetylenedicarboxylates, which was catalyzed by a rhodium(i)-chiral phosphoramidite complex, was developed. This protocol provided a highly enantioselective access to prepare carbonyl substituted cyclohexa-1,4-dienes with up to 96% yield and >99% ee. Notably, a cycloaddition on the 10 g scale gave the product in 92% yield and with 99% ee, which showed great potential for the scale-up synthesis of carbonyl substituted cyclohexa-1,4-dienes. In addition, oxidative aromatizations and hydrolysis of the products were also investigated.
手性膦酰胺配体铑（I）催化的 1,3-二烯与二烷基丙二炔酸酯的不对称分子间[4+2]环加成反应得到了发展。该方法为合成羰基取代的环己-1,4-二烯提供了一种高对映选择性的方法，产率高达 96%，对映选择性大于 99%。值得注意的是，在 10 克规模的环加成反应中，产物的收率为 92%，对映选择性为 99%，这表明该方法在羰基取代的环己-1,4-二烯的放大合成中具有很大的潜力。此外，还对产物的氧化芳构化和水解进行了研究。
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