氯化铁催化氮杂七富烯与双环[1.1.0]丁烷的分子间形式[8π + 2σ]环加成反应合成环庚三烯稠合的2-氮杂双环[3.1.1]庚烷
FeCl-Catalyzed Intermolecular Formal [8π+2σ] Cycloaddition of Azaheptafulvene with Bicyclo[1.1.0]butanes for the Synthesis of Cycloheptatriene-Fused 2-Azabicyclo[3.1.1]heptanes.
作者信息
Zhu Shijie, Lei Jiaojiao, Yang Shengwen, Zhao Zhifei, Liu Ning, Li Shi-Wu
机构信息
School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003, China.
School of Pharmacy/Key Laboratory of Xinjiang Endemic Phytomedicine Resources Ministry of Education, Shihezi University, Shihezi, Xinjiang 832003, China.
出版信息
Org Lett. 2025 Apr 18;27(15):3831-3837. doi: 10.1021/acs.orglett.5c00489. Epub 2025 Apr 8.
Higher-order cycloadditions are a simple and effective strategy for constructing significant medium-sized architectures. Azaheptafulvenes reacting with readily accessible bicyclo[1.1.0]butanes (BCBs) through FeCl-promoted intermolecular formal [8π+2σ] cycloaddition reactions to access cycloheptatriene-fused 2-azabicyclo[3.1.1]heptanes have been developed. This new reaction tolerated a wide range of azaheptafulvenes and BCBs. Furthermore, the amplification experiment and synthetic transformations of the adducts, including modifications of marketed drugs, further highlighted their practicalities. Control experiments and DFT calculations suggest that the diastereoselective [8π+2σ] product formation may involve a stepwise pathway.
高阶环加成反应是构建重要中等尺寸结构的一种简单有效的策略。已开发出氮杂庚搭烯通过氯化铁促进的分子间形式[8π + 2σ]环加成反应与易于获得的双环[1.1.0]丁烷（BCB）反应，以得到环庚三烯稠合的2-氮杂双环[3.1.1]庚烷。这种新反应能耐受多种氮杂庚搭烯和BCB。此外，加合物的放大实验和合成转化，包括市售药物的修饰，进一步突出了它们的实用性。对照实验和密度泛函理论计算表明，非对映选择性[8π + 2σ]产物的形成可能涉及逐步途径。
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