Xue Sijing, Lücht Alexander, Benet-Buchholz Jordi, Kleij Arjan W
Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 -, Tarragona, Spain.
Catalan Institute of Research and Advanced Studies (ICREA), Pg. Lluís Companys 23, 08010, Barcelona, Spain.
Chemistry. 2021 Jul 12;27(39):10107-10114. doi: 10.1002/chem.202100677. Epub 2021 Jun 2.
The challenging metal-catalyzed asymmetric synthesis of highly functional quaternary carbon centers using decarboxylative C(sp )-C(sp ) bond formation reactions is reported. The key substrate, a vinyl cyclic carbonate, is activated to provide concomitantly both the requisite nucleophile (by formal umpolung) and electrophile reaction partner preceding the asymmetric cross-coupling process. A wide screening of reaction conditions, additives and catalyst precursors afforded a protocol that gave access to a series of compounds featuring densely functionalized, elusive quaternary carbon stereocenters in appreciable yield and with enantiomeric ratios (er's) of up to 90 : 10.
报道了使用脱羧C(sp³)-C(sp³)键形成反应进行具有挑战性的金属催化的高官能度季碳中心的不对称合成。关键底物乙烯基环状碳酸酯被活化，以在不对称交叉偶联过程之前同时提供所需的亲核试剂（通过形式上的极性翻转）和亲电反应伙伴。对反应条件、添加剂和催化剂前体进行了广泛筛选，得到了一种方法，该方法能够以可观的产率和高达90:10的对映体比例（er值）获得一系列具有密集官能化、难以捉摸的季碳立体中心的化合物。
