Department of Pharmaceutical Sciences, Faculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato-ku, Tokyo 105-8512, Japan.
Chem Commun (Camb). 2020 Mar 26;56(25):3621-3624. doi: 10.1039/d0cc01017k.
A stepwise dehydrogenative cross-coupling method was developed for the formation of sterically hindered Csp3-Csp3 bonds. Intramolecular dehydrogenative O-alkylation of a β-ketoester by 2,3-dichloro-5,6-dicyano-p-benzoquinone to form an oxolane followed by Lewis acid-catalyzed [1,3]-rearrangement furnished the sesquiterpene arylmethylcyclopentane skeleton. The formal syntheses of herbertane-type β-herbertenol, cuparane-type enokipodins A and B were also achieved.
发展了一种逐步脱氢交叉偶联方法，用于形成空间位阻的 Csp3-Csp3 键。β-酮酯通过 2,3-二氯-5,6-二氰基对苯醌进行分子内脱氢 O-烷基化形成恶唑烷，然后路易斯酸催化[1,3]-重排，生成倍半萜芳基甲基环戊烷骨架。还实现了 herbertane 型 β-herbertenol、cuparane 型 enokipodins A 和 B 的形式合成。
