Daphenylline, a structurally unique triterpenoid Daphniphyllum alkaloid, has attracted considerable attention from the synthetic community since its isolation. Herein, we delineate an enantioselective total synthesis of (‐)‐daphenylline, which is based on a gold‐catalyzed dearomatization reaction of β‐methoxynaphthalene. Other features include installation of the initial chiral stereocenter via an enantioselective rhodium‐catalyzed hydrogenation of an indene derivative; construction of the other vital stereocenter by organocatalytic asymmetric Mukaiyama–Michael reaction of a structurally complex benzofused cyclohexanone; and a tandem reductive amination/amidation double cyclization reaction to assemble the distinctive azapolycyclic cage‐like architecture.

中文翻译：

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金催化甲氧基萘分子内脱芳构反应全合成(-)-达苯啉


Daphenline 是一种结构独特的三萜类 Daphniphyllum 生物碱，自分离以来引起了合成界的广泛关注。在此，我们描述了(-)-达苯啉的对映选择性全合成，该合成基于金催化的β-甲氧基萘的脱芳构化反应。其他特征包括通过茚衍生物的对映选择性铑催化氢化安装初始手性立体中心；通过结构复杂的苯并稠合环己酮的有机催化不对称 Mukaiyama-Michael 反应构建另一个重要的立构中心；以及串联还原胺化/酰胺化双环化反应来组装独特的氮杂多环笼状结构。