文献类型：期刊文献

英文题名：Asymmetric Dearomatization of Nonfunctionalized 1-Naphthols via Copper-Catalyzed Enantioselective [4+1] Spiroannulation

作者：Li, Xingguang[1];Guo, Jia-Xing[1];Zhang, Jin[2,3];Chen, Qian-Yu[1];He, Yu-Jie[1];Sha, Feng[1];Xiang, Huijing[5];Yu, Peiyuan[2,3];Liu, Pei-Nian[1,4]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai Key Lab Funct Mat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China;[3]Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China;[4]China Pharmaceut Univ, Sch Pharm, State Key Lab Nat Med, Nanjing 210009, Peoples R China;[5]Shanghai Univ, Sch Life Sci, Shanghai 200444, Peoples R China

年份：2024

卷号：14

期号：12

起止页码：9244

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20242316220623);WOS:【SCI-EXPANDED(收录号:WOS:001238269200001)】；

基金：This work was supported by the National Natural Science Foundation of China (Nos. 22201073, 21925201, 22161160319, T2322018, and 32171391) and the Fundamental Research Funds for the Central Universities. We thank the Research Center of Analysis and Test of East China University of Science and Technology for help in the characterization.

语种：英文

外文关键词：dearomatization; nonfunctionalized 1-naphthol; spiroannulation; stereoselectivity; copper catalysis

摘要：Catalytic asymmetric dearomatization (CADA) is a powerful tool for the rapid construction of complex chiral three-dimensional cyclic molecules featuring quaternary carbon centers from readily available arenes. However, the asymmetric dearomatization of ubiquitous nonfunctionalized 1-naphthols to afford chiral quaternary centers remains challenging and undeveloped. This study reports the asymmetric dearomative [4 + 1] spiroannulation of nonfunctionalized 1-naphthols via copper catalysis. This reaction features a highly chemo-, regio-, and stereoselective nucleophilic addition and intramolecular annulation cascade of a reactive pi-extended copper-allenylidene, thus enabling the practical synthesis of a range of valuable spirocyclic enones bearing a chiral quaternary stereocenter with high efficiency. Furthermore, this protocol is applicable to phenols. Control experiments supported the substitution-annulation cascade mechanism by excluding a process involving a 1,3-sigmatropic shift. Preliminary biological activity studies indicated that the synthesized spirocyclic enones hold significant promise as anticancer agents by inducing tumor cell apoptosis.