Enantioselective Total Synthesis of (-)-Caldaphnidine O via a Radical Cyclization Cascade

Journal of the American Chemical Society
Lian-Dong GuoJing Xu

Abstract

The synthetically challenging, diverse chemical skeletons and promising biological profiles of the Daphniphyllum alkaloids have generated intense interest from the synthetic chemistry community. Herein, the first and enantioselective total synthesis of (-)-caldaphnidine O, a complex bukittinggine-type Daphniphyllum alkaloid, is described. The key transformations in this concise approach included an intramolecular aza-Michael addition, a ring expansion reaction sequence, a Sm(II)/Fe(III)-mediated Kagan-Molander coupling, and the rapid formation of the entire hexacyclic ring skeleton of the target molecule via a radical cyclization cascade reaction, which was inspired by an unexpected radical detosylation observed in our recent dapholdhamine B synthesis.

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Citations

Dec 10, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Stefano NejrottiCristina Prandi
Mar 7, 2021·Journal of Industrial Microbiology & Biotechnology·Yuxuan YeTodd K Hyster
Sep 20, 2019·The Journal of Organic Chemistry·Cedric L HugelshoferRichmond Sarpong
Aug 20, 2020·Journal of the American Chemical Society·Guangpeng XuChao Li
Aug 21, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·María Sánchez-RosellóCarlos Del Pozo
Oct 20, 2020·Accounts of Chemical Research·Lian-Dong GuoJing Xu

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