N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Academician Lavrentyev Ave, 9, 630090 Novosibirsk, Russia.
Molecules. 2022 Apr 20;27(9):2643. doi: 10.3390/molecules27092643.
Isospongian diterpenes are a small but growing family of natural tetracyclic secondary metabolites isolated from marine organisms, primarily sponges and nudibranchs. A palladium-catalyzed domino Heck-Suzuki reaction sequence for the synthesis of the tetracyclic skeleton of marginatafuran-type isospongian diterpenoids with a wide variety of substituents in the C-17 position is reported. The proposed approach was based on selective transformations of the accessible plant diterpenoid lambertianic acid and includes an intramolecular Heck reaction of 16-bromolambertianic and arylation of the palladium intermediate with arylboronic acid. The influence of the nature of the substituent both in arylboronic acids and in the furan ring of 16-bromolambertianic acid on the direction and chemoselectivity of the reaction has been studied. The described derivatization of natural furanolabdanoid lambertianic acid produced new functionalized molecules for biological study and gave novel insights into the reactivity of complex molecular structures.
异海绵二萜是一类从小但不断增长的天然四环次级代谢产物家族，从海洋生物中分离得到，主要是海绵和裸鳃类动物。本文报道了钯催化的串联 Heck-Suzuki 反应序列，用于合成具有广泛取代基的边缘呋喃型异海绵二萜的四环骨架，这些取代基位于 C-17 位。该方法基于可及植物二萜 Lambertianic 酸的选择性转化，包括 16-溴 Lambertianic 酸的分子内 Heck 反应和钯中间体与芳基硼酸的芳基化。研究了芳基硼酸和 16-溴 Lambertianic 酸中呋喃环上取代基的性质对反应方向和化学选择性的影响。对天然呋喃 Labdanoid Lambertianic 酸的这种衍生化产生了用于生物学研究的新官能化分子，并深入了解了复杂分子结构的反应性。
