Department of Chemistry, Chonnam National University, Gwangju 61186, Republic of Korea.
J Org Chem. 2020 Nov 6;85(21):14246-14252. doi: 10.1021/acs.joc.0c02194. Epub 2020 Oct 28.
A synthesis of (+)-hypoxylactone has been accomplished in four steps starting from the allenoate γ-addition of -3-chloro-2-silyoxybutanals, leading to the revision of stereochemistry. The key was the discovery of control elements required to matching/mismatching cases in the allenoate γ-addition to provide the desired adducts as a single isomer. The utility of the γ-adduct was demonstrated with the Au(I)-catalyzed cyclization to afford (+)-xylogiblactone A. Use of AgO was the key to epoxidation for preventing epimerization of the γ-lactone ring.
（+）-Hypoxylactone 的合成就从 -3-氯-2-硅氧基丁醛的烯丙酸盐γ-加成开始，通过 4 步反应完成，从而修正了立体化学。关键是发现了控制元素，这些元素在烯丙酸盐γ-加成中需要匹配/不匹配情况，以提供所需的加成物作为单一异构体。γ-加成物的用途通过 Au(I)-催化的环化反应得到（+）-木罗糖基 giblactone A 得到了证明。使用 AgO 进行环氧化是防止γ-内酯环消旋化的关键。
