Example：10.1021/acsami.1c06204 or Chem. Rev., 2007, 107, 2411-2502
Dibenzocycloheptanones construction through a removable P-centered radical: synthesis of allocolchicine analogues Chemical Science (IF9.825), Pub Date : 2021-11-09, DOI: 10.1039/d1sc05404j Yan Zhang, Zhenzhi Cai, Julia Struwe, Chanchan Ma, Wangyu Zeng, Xinyi Liao, Min Xu, Lutz Ackermann
Dibenzocycloheptanones containing a tricyclic 6–7–6-system are present in numerous biologically active natural molecules. However, the simple and efficient preparation of derivatives containing a dibenzocycloheptanone scaffold remains difficult to date. Herein, we report a versatile strategy for the construction of these challenging seven-membered rings using a 7-endo-trig cyclization which is initiated by a phosphorus-centered radical. This approach provides a step-economical regime for the facile assembly of a wide range of phosphorylated dibenzocycloheptanones. Remarkably, we also have devised a traceless addition/exchange strategy for the preparation of dephosphorylated products at room temperature with excellent yields. Therefore, this protocol allows for the concise synthesis of biorelevant allocochicine derivatives.