Yang Chen, Hui Yan, Hanliang Zheng, Wei-Ping Deng, Zhong Li, Wu-Lin Yang
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Ir/Brønsted acid dual-catalyzed asymmetric synthesis of bisbenzannulated spiroketals and spiroaminals from isochroman ketals
Herein, we reported an Ir/Brønsted 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 Brønsted 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 Brønsted 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.
期刊介绍:
Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.