Ir/Bronsted acid dual-catalyzed asymmetric synthesis of bisbenzannulated spiroketals and spiroaminals from isochroman ketals

被引:1
作者
Chen, Yang [1 ]
Yan, Hui [1 ]
Zheng, Hanliang [2 ]
Deng, Wei-Ping [2 ]
Li, Zhong [1 ]
Yang, Wu-Lin [1 ]
机构
[1] East China Univ Sci & Technol, Shanghai Key Lab Chem Biol & Sch Pharm, 130 Meilong Rd, Shanghai 200237, Peoples R China
[2] Zhejiang Normal Univ, Coll Chem & Mat Sci, Key Lab Minist Educ Adv Catalysis Mat, Jinhua 321004, Peoples R China
来源
ORGANIC CHEMISTRY FRONTIERS | 2024年 / 11卷 / 20期
基金
中国国家自然科学基金; 上海市自然科学基金;
关键词
ALLYLIC SUBSTITUTION-REACTIONS; ENANTIOSELECTIVE SYNTHESIS; BENZYLIC ETHERS; CYCLOADDITION; FUNCTIONALIZATION; CONSTRUCTION; ALKYLATION; PROGRESS;
D O I
10.1039/d4qo01402b
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Herein, we reported an Ir/Br & oslash;nsted acid dual-catalyzed asymmetric cascade reaction of 2-(1-hydroxyallyl)-phenols with isochroman ketals to produce bisbenzannulated spiroketals in high efficiency with generally high diastereo- and enantioselectivities (up to 17 : 1 dr, >99% ee). The procedure involved the generation of exocyclic enol ethers from isochroman ketals through Bronsted acid catalysis, followed by an Ir-catalyzed enantioselective allylation/spiroketalization sequence with 2-(1-hydroxyallyl)-phenols. Mechanistic investigations and theoretical calculations revealed that chiral iridium catalyst controlled the enantioselectivity, while the high diastereoselectivity was attributed to a Br & oslash;nsted acid-promoted thermodynamically controlled epimerization process. Furthermore, the asymmetric cascade reaction involving 2-(1-hydroxyallyl)anilines was found to be applicable for synthesizing optically pure bisbenzannulated spiroaminals. Additionally, some of the bisbenzannulated spiroketal products showed promising inhibitory activity against Rhizoctonia solani, suggesting their potential applications in agrochemical discovery.
引用
收藏
页码:5831 / 5840
页数:10
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