The 6,8-dioxabicyclo[3.2.1]octane (6,8-DOBCO) architecture widely exists in a broad spectrum of bioactive natural products, and the development of efficient and convenient protocols to construct this skeleton remains a challenging task. Here, we report a concise synthetic strategy for the single-step construction of 6,8-DOBCO frameworks from simple vinylethylene carbonates and amine-substituted enones. This protocol features a sequential reaction of N-allylic substitution, Diels–Alder cyclization, and intramolecular ketalization, which is promoted by metal-organo relay catalysis involving palladium/phosphoric acid or palladium/halogen-bonding catalytic system. Over 50 examples of 6,8-DOBCO derivatives with structural diversity have been facilely achieved with satisfactory synthetic results, including high levels of stereoselectivity, reasonable isolated yield, ample scope in reaction partners, high step economy, and operational simplicity.

中文翻译：

---

碳酸乙烯乙烯酯经钯-有机催化剂的非对映选择性构建6,8-二氧杂双环[3.2.1]辛烷骨架

6,8-二氧杂双环[3.2.1]辛烷（6,8-DOBCO）结构广泛存在于多种生物活性天然产物中，开发有效且方便的方案以构建该骨架仍然是一项艰巨的任务。在这里，我们报告了从简单的乙烯基碳酸乙烯酯和胺取代的烯酮一步一步构建6,8-DOBCO骨架的简明合成策略。该协议具有N的顺序反应-烯丙基取代，Diels-Alder环化和分子内缩酮化，这是通过涉及钯/磷酸或钯/卤素键合催化体系的金属-有机中继催化作用而促进的。已轻松实现了50多个具有结构多样性的6,8-DOBCO衍生物实例，并获得了令人满意的合成结果，包括高水平的立体选择性，合理的分离得率，反应伙伴中的化合物范围广，步骤经济性高和操作简便等优点。