Institut für Organische Chemie, Eberhard Karls Universität Tübingen , Auf der Morgenstelle 18, 72076 Tübingen, Germany.
J Org Chem. 2017 Sep 15;82(18):9844-9850. doi: 10.1021/acs.joc.7b01416. Epub 2017 Aug 29.
The polycyclic natural product lingzhiol [(±)-1] was synthesized from dimethoxytetralone 8 via cyclization of an intermediate benzylic radical, generated from spiroepoxide 14, onto an alkynyl substituent generating tetracyclic compound 13 with an exocyclic double bond. After oxidative cleavage of the double bond of 13 and reduction of the keto function of 23, the correct diastereomer, 12-syn, was converted to lingzhiol (1) via known steps. In a similar manner, lingzhiol analogue 39 was synthesized from 5-methoxy-1-tetralone (27).
多环天然产物灵枝醇[(±)-1]是通过中间体苄基自由基的环化反应从二甲氧基四氢萘酮 8 合成的，该自由基是由螺环环氧 14 生成的，然后与炔基取代基反应生成具有环外双键的四环化合物 13。13 的双键经过氧化裂解和 23 的酮官能团还原后，通过已知步骤将正确的非对映异构体 12-syn 转化为灵枝醇(1)。以类似的方式，从 5-甲氧基-1-四氢萘酮(27)合成了灵枝醇类似物 39。
