Abstract
A chiral phosphoric acid catalyzed enantioselective [2 + 2] cycloaddition of alkynylindols or alkynylnaphthols with quinones is disclosed. A class of functionalized cyclobutenes with excellent yields, diastereo- and enantioselectivities were prepared under mild reaction conditions (70 examples, up to 99% yield, 99% ee, all > 50:1 dr). Mechanistic studies revealed that a dearomatization of indole or naphthol occurred to initiate the cycloaddition, followed by an intramolecular Michael addition with in situ generated allene-iminium or vinylidene-quinone methide intermediate. The competitive [2 + 3] cycloaddition was prevented in this catalytic system. An interesting central to axial chirality conversion via a rearrangement process was realized during transformation of the product.
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CCDC 2130886 (3d), 2175084 (3q), 2254781 (3as), 2174883 (6a′) and 2208602 (16b) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (NSFC 21672170), the Natural Science Basic Research Plan in Shaanxi Province of China (2021JZ-40), and Shaanxi Fundamental Science Research Project for Chemistry & Biology (22JHQ007). The calculations were performed at Chemical HPC Center of NWU.
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Sun, HR., Yang, L., Li, Y. et al. Organocatalytic asymmetric [2 + 2] cycloaddition of alkynes with quinones. Sci. China Chem. 66, 2292–2299 (2023). https://doi.org/10.1007/s11426-023-1658-9
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DOI: https://doi.org/10.1007/s11426-023-1658-9