Regio‐ and Stereoselective Cascade of β,γ‐Unsaturated Ketones by Dipeptided Phosphonium Salt Catalysis: Stereospecific Construction of Dihydrofuro‐Fused [2,3‐b] Skeletons
- 2 July 2021
- journal article
- research article
- Published by Wiley in Angewandte Chemie
- Vol. 60 (36), 19860-19870
- https://doi.org/10.1002/anie.202106046
Abstract
Chiral (dihydro)furo-fused heterocycles are significant structural motifs in numerous natural products, functional materials and pharmaceuticals. Therefore, developing efficient methods for preparing compounds with these privileged scaffolds is an important endeavor in synthetic chemistry. Herein, we develop an effective, modular method by a dipeptide-phosphonium salt-catalyzed regio- and stereoselective cascade reaction of readily available linear β,γ-unsaturated ketones with aromatic alkenes, affording a wide variety of structurally fused heterocyclic molecules in high yields with excellent stereoselectivities. Of note, this method provides a platform for building three types of valuable dihydrofuro-fused rigid tricyclic architectures that have great synthetic challenges. Moreover, mechanistic investigations revealed that the bifunctional phosphonium salt catalyst controlled the regio- and stereoselectivities of this cascade transformation, particularly proceeding through the initial ketone α-addition followed by O -participated substitution; and the multiple hydrogen-bonding interactions between Brønsted acid moieties of catalyst and nitro group of aromatic alkene were crucial in asymmetric induction. Given the generality, versatility, and high efficiency of this method, we anticipate that it will have broad synthetic utilities.Funding Information
- National Natural Science Foundation of China (21971165, 21921002)
- Fundamental Research Funds for the Central Universities (N.A.)
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