Graduate School of Pharmaceutical Sciences, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan.
Graduate School of Pharmaceutical Sciences, University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Org Lett. 2017 Nov 3;19(21):5833-5835. doi: 10.1021/acs.orglett.7b02812.
A synthesis of cardiopetaline has been accomplished via a Wagner-Meerwein rearrangement of a diol having the denudatine skeleton. The Wagner-Meerwein rearrangement could be facilitated simply by heating the diol with p-toluenesulfonic acid in pivalic acid, without preactivating the pivotal hydroxy group. This strategy does not require differentiation of several hydroxy groups in the substrate for the Wagner-Meerwein rearrangement and could be applied to the synthesis of more highly oxygenated aconitine-type diterpenoid alkaloids.
通过对具有 denudatine 骨架的二醇进行 Wagner-Meerwein 重排，合成了 cardiopetaline。通过将二醇与对甲苯磺酸在特戊酸中加热，无需预先活化关键羟基，即可简单地促进 Wagner-Meerwein 重排。该策略不需要对 Wagner-Meerwein 重排的底物中的几个羟基进行区分，并且可以应用于合成更高度氧化的乌头型二萜生物碱。
