ICIQ - Institute of Chemical Research of Catalonia, The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain.
Department of Analytical Chemistry and Organic Chemistry, University Rovira i Virgili, 43007 Tarragona, Spain.
Org Lett. 2022 Mar 4;24(8):1695-1699. doi: 10.1021/acs.orglett.2c00326. Epub 2022 Feb 24.
We describe an asymmetric organocatalytic method to synthesize 1,7-dicarbonyl compounds containing a β-stereocenter. The chemistry relies on the formation of γ-keto radicals, generated upon oxidative ring opening of cyclobutanols mastered by an organic photoredox catalyst. These nonstabilized primary radicals are stereoselectively intercepted by an iminium ion intermediate, formed upon activation of aliphatic and aromatic enals by a chiral secondary amine catalyst. This organocatalytic photoredox method served to prepare scaffolds found in natural products and drug molecules.
我们描述了一种不对称的有机催化方法，用于合成含有β-立体中心的 1,7-二羰基化合物。该化学方法依赖于环丁醇经有机光氧化还原催化剂氧化开环生成γ-酮自由基，这些未稳定的初级自由基被手性仲胺催化剂活化的脂肪族和芳香族烯醛形成的亚胺离子中间体立体选择性捕获。这种有机催化的光氧化还原方法可用于制备天然产物和药物分子中的支架结构。
