Experimental and Computational Analysis of the Solution and Solid-State Conformations of Hexadepsipeptides from Beauveria felina  

作　　者：Feng-Yu Du Attila Mandi Xiao-Ming Li Ling-Hong Meng Tibor Kurtan Bin-Gui Wang 

机构地区：[1]CAS&Shandong Province Key Laboratory of Experimental Marine Biology,Institute of Oceanology,Chinese Academy of Sciences,and Laboratory of Marine Biology and Biotechnology,Qingdao National Laboratory for Marine Science and Technology,Nonhoi Rood 7,Qingdao,Shandong 266071,China [2]College of Chemistry and Pharmacy,Qingdao Agricultural University,Qingdoo,Shandong 266109,China [3]Department of Organic Chemistry,University of Debrecen,POB 400,4002 Debrecen,Hungary [4]College of Marine Science,University of Chinese Academy of Sciences,Yuquon Rood 19A,Beijing 100049,China [5]Center for Ocean Mego-Science,Chinese Academy of Sciences,Nonhoi Road 7t Qingdao,Shandong 266071,China

出　　处：《Chinese Journal of Chemistry》2022年第3期378-384,共7页中国化学（英文版）

基　　金：the National Natural Science Foundation of China(31270104);the NSFC-Shandong Joint Fund for Marine Science Research Centers(U1606403);the Oceanographic Data Center at IOCAS.T.K.and A.M.thank the National Research,Development and Innovation Office(NKFI K120181 and FK134653);the Governmental Information-Technology Development Agency(KIFU for CPU time);B.-G.W.also acknowledged the support of the Taishan Scholar project from Shandong province.

摘　　要：Chemical investigation of Beouverio felina,a marine-derived entomopathogenic fungus,obtained two new destruxin hexadepsipeptides(1 and 2)containing an/.-Ala^(5)residue instead of the usual A/-Me-L-Ala^(5).Interestingly,the presence of the/.-Ala^(5)residue enabled two slowly-exchanging solution conformers with cis/trons(ILE^(3))-(A/-Me-Val^(4))amide bond for 1 and 2 with 1.5:1 and 1:1 cis/trans ratios,respectively,while only the conformer with c/s amide bond was found in the solid-state.The solution and solid-state conformers were studied by NMR,X-ray diffraction and solution and solid-state ECD measurements,as well as by TDDFT-ECD calculations.Structural(conformational)parameter-activity correlations suggested that the extended destruxin geometry with the preferred c/s(ILE^(3))-(A/-Me-Val^(4))bond probably resulted in improved bioactivity and reduced toxicity for the destruxin class.This was the first report on the interconversion phenomenon of cis/trans amide bonds of destruxin class,which could give insights in the development of bioactive destruxin agents with lower toxicity.

关 键 词：Beouveria felina Natural products Destruxin hexadepsipeptides Structure elucidation Conformation analysis 

分 类 号：O62[理学—有机化学]