The Research Center of Chiral Drugs, Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, 1200 Cailun Road, Shanghai 201203, China.
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
Org Lett. 2020 Jun 5;22(11):4300-4305. doi: 10.1021/acs.orglett.0c01339. Epub 2020 May 26.
An efficient one-pot synthesis of multisubstituted 9,10-dihydrophenanthrenes from easily available 2-arylazaarenes and cyclohexadienone-tethered terminal alkynes (1,6-enynes) has been successfully achieved. This domino reaction proceeded smoothly through Cp*Rh(III)-catalyzed C-H activation, direct protonation of alkenyl-Rh intermediates, intramolecular Diels-Alder reaction, alkene isomerization, subsequent ring-opening aromatization, and acetylation. This strategy was pot-economical and tolerated a wide range of functional groups. Moreover, the potent anticancer activities against HepG2 cells were observed for these artificial 9,10-dihydrophenanthrene derivatives.
一种高效的一锅法合成多取代的 9,10-二氢菲，是由易得的 2-芳基氮杂芳烃和环已二烯酮-连接的末端炔烃（1,6-烯炔）合成的。该串联反应通过 Cp*Rh（III）催化的 C-H 活化、烯基-Rh 中间体的直接质子化、分子内 Diels-Alder 反应、烯烃异构化、随后的开环芳构化和乙酰化顺利进行。该策略具有节约成本的优势，并能耐受广泛的官能团。此外，这些人工 9,10-二氢菲衍生物对 HepG2 细胞表现出很强的抗癌活性。
