Four new N-acylated aminoalkanoic acids,namely clonoroseins E−H(1−4),together with three previously identified analogs,clonoroseins A,B,and D(5−7),were identified from the endophytic fungus Clonostachys rosea strain 1...Four new N-acylated aminoalkanoic acids,namely clonoroseins E−H(1−4),together with three previously identified analogs,clonoroseins A,B,and D(5−7),were identified from the endophytic fungus Clonostachys rosea strain 15020(CR15020),using Feature-based Molecular Networking(FBMN).The elucidation of their chemical structures,including their absolute configurations,was achieved through spectroscopic analysis combined with quantum chemical calculations.Bioinformatics analyses suggested that an iterative type I HR-PKS(CrsE)generates the polyketide side chain of these clonoroseins.Furthermore,a downstream adenylate-forming enzyme of the PKS(CrsD)was suspected to function as an amide synthetase.CrsD potentially facilitates the transformation of the polyketide moiety into an acyl-AMP intermediate,followed by nucleophilic substitution with eitherβ-alanine orγ-aminobutyric acid to produce amide derivatives.These findings significantly expand our understanding of PKS-related products originating from C.rosea and also underscore the powerful application of FBMN analytical methods in characterization of new compounds.展开更多
基金support from the National Key Research and Development Program of China(2019YFA0906200)the National Natural Science Foundation of China(21977029,81903529,21877038,31720103901,and 81573341)the Open Project Funding of the State Key Laboratory of Bioreactor Engineering,the 111 Project(B18022).
文摘Four new N-acylated aminoalkanoic acids,namely clonoroseins E−H(1−4),together with three previously identified analogs,clonoroseins A,B,and D(5−7),were identified from the endophytic fungus Clonostachys rosea strain 15020(CR15020),using Feature-based Molecular Networking(FBMN).The elucidation of their chemical structures,including their absolute configurations,was achieved through spectroscopic analysis combined with quantum chemical calculations.Bioinformatics analyses suggested that an iterative type I HR-PKS(CrsE)generates the polyketide side chain of these clonoroseins.Furthermore,a downstream adenylate-forming enzyme of the PKS(CrsD)was suspected to function as an amide synthetase.CrsD potentially facilitates the transformation of the polyketide moiety into an acyl-AMP intermediate,followed by nucleophilic substitution with eitherβ-alanine orγ-aminobutyric acid to produce amide derivatives.These findings significantly expand our understanding of PKS-related products originating from C.rosea and also underscore the powerful application of FBMN analytical methods in characterization of new compounds.
