Organic and Medicinal Chemistry Division, CSIR-Indian Institute of Chemical Biology, 4-Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India.
Chem Commun (Camb). 2023 Jun 20;59(50):7751-7754. doi: 10.1039/d3cc01416a.
We report an unprecedented atom-economic one-pot Cp*Rh(III)-catalyzed regioselective [3+2]-spiroannulation reaction between dibenz(ox)azepines and ynones, allowing the synthesis of biologically relevant novel spirocyclic dibenz(ox)azepines under operationally simple and mild reaction conditions. The reaction proceeds without any silver additive or external oxidant implementing a redox-neutral pathway. A broad substrate scope with diverse functional group tolerance permitted the regioselective synthesis of a wide spectrum of indene-containing spirocyclic dibenz(ox)azepines in good to excellent yields. Also, we showcased detailed mechanistic studies to justify the formation of spirocycles. In addition, the synthetic utility of this process was also demonstrated by the modular synthesis of various steroid conjugates.
我们报告了一种前所未有的原子经济性一锅法 Cp*Rh(III)催化的二苯并[ox]氮杂卓和炔酮之间的区域选择性[3+2]-螺环化反应，在操作简单温和的反应条件下允许合成具有生物相关性的新型螺环二苯并[ox]氮杂卓。该反应在没有任何银添加剂或外部氧化剂的情况下进行，采用了氧化还原中性途径。广泛的底物范围和对各种官能团的耐受性允许在良好到优秀的收率下区域选择性合成广泛的含茚螺环二苯并[ox]氮杂卓。此外，我们还展示了详细的机理研究来证明螺环的形成。此外，该过程的合成实用性还通过各种甾体缀合物的模块化合成得到了证明。
