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Asymmetric Total Synthesis of (−)-Lycospidine A

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posted on 2016-08-26, 20:14 authored by Shiyan Xu, Jing Zhang, Donghui Ma, Dengyu Xu, Xingang Xie, Xuegong She
The first asymmetric total synthesis of the structurally unique Lycopodium alkaloid (−)-lycospidine A, containing an unprecedented five-membered ring, has been accomplished in only 10 steps with 21.6% overall yield from the known conveniently available sulfoxide. This protecting-group-free short synthesis relied on the use of a key amidation/aza-Prins domino cyclization reaction to rapidly construct the tricyclic skeleton and two continuous stereocenters (one of which is a bridged quaternary stereocenter). An intramolecular aldol condensation was successfully utilized to establish the unique five-membered ring, and a late-stage oxidation inspired by biosynthesis pathway was adopted to synthesize the diosphenol ring of (−)-lycospidine A.

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