Institute of Medicinal Plant Development, Chinese Academy of Medical Science and Peking Union Medical College, Beijing 100193, P. R. China.
School of Biotechnology and Health Sciences, Wuyi University, Jiangmen 529020, P. R. China.
Org Lett. 2020 Apr 17;22(8):3200-3204. doi: 10.1021/acs.orglett.0c00970. Epub 2020 Apr 8.
Palladium-catalyzed dearomative [2+2+1] annulations of aryl ethers with alkynes are reported via -selective C-H functionalization, providing highly functionalized spirocyclohexadienones in moderate to excellent yields under mild reaction conditions. Importantly, mechanistic investigation indicated an unusual C-O bond cleavage was involved. Moreover, polyarylated naphthalenes could be obtained via oxidative [2+2+2] annulation by tuning aryl ethers from monomethoxybenzenes to polymethoxybenzenes under an identical catalytic system.
报道了钯催化的芳基醚与炔烃的去芳构化[2+2+1]环加成反应，通过 -选择性 C-H 官能化，在温和的反应条件下以中等至优异的收率得到了高度官能化的螺环环己二烯酮。重要的是，机理研究表明涉及到不寻常的 C-O 键断裂。此外，通过在相同的催化体系中，将芳基醚从单甲氧基苯调变为多甲氧基苯，可以通过氧化[2+2+2]环加成得到多芳基化的萘。
