Nematicidal Epipolysulfanyldioxopiperazines from Gliocladium roseum

Abstract

Five new verticillin-type epipolysulfanyldioxopiperazines, gliocladine A (1), B (2), C (3), D (4), and E (5), were isolated from wheat solid-substrate fermentation of Gliocladium roseum 1A, along with four known compounds, verticillin A (6), 11'-deoxyverticillin A (7), Sch52900 (8), and Sch52901 (9). Their structures were elucidated by extensive 1D and 2D NMR studies, MS, and chemical transformations. In vitro immersion tests showed that all nine compounds exhibited antinematodal activity against Caenorhabditis elegans and Panagrellus redivivus. The monomeric epipolysulfanydioxopiperazines (3-5), with the indole moiety, were found to be less active than the dimeric compounds (1, 2, 6-8).

Structure, Bioactivity and Synthesis of Natural Products with Hexahydropyrrolo[2,3‐b]indole

“…[16][17][18][19][20][21][22] In okaramines the HPIC is condensed to a diketopiperazine (DKP) unit formed from a second amino acid. Leptosins D-F (12)(13)(14), [23] gliocladines C-E (15-17), [24] gliocladins A-C, [25] plectosphaeroic acids A-C (18,19), [26] (+)-asperazine (20), [27] and naseseazines A and B [28] have an analogous DKP unit containing an extra indole, bound between C 3 and C 3a (except for in the case of (+)-asperazine and the naseseazines, in which the indole binds via C 7 and C 6 , respectively). Brevicompanines A-H (21: A, 22: B), allo-brevicompanine B and fructigenine B [29][30][31] are also alkylated at C 3a ; as is ardeemin, isolated from a strain of Aspergillus fischeri; [32] roquefortines C, D (23), F and G; [33][34][35][36] and aszonalenin (24).…”

“…These include the neurokinin antagonists (+)-WIN64 821 (38) and (+)-WIN64 745 (39), both isolated from a strain of Aspergillus sp. ; [64][65][66] (À)-ditryptophenaline (40), obtained from Aspergillus flavus; [67] the antiviral agent (+)-asperdimin (41), isolated from extracts of Aspergillus niger; [68] chaetocin (42), isolated from the fermentation broth of Chaetomium minutum; [69] verticillins A (43), B, and C, obtained from Verticillium sp., exhibit antimicrobial activity against Gram-positive bacteria and potent antitumor activity in HeLa cell lines; [70][71][72] gliocladines A (44) and B (45); [24] 11,11'-dideoxyverticillin A and 11'-deoxyverticillin A; [24,73] melinacidins; [74][75][76] Sch52 900 and Sch52 901; [24] and some leptosins A (46), B (47), and C (48). [23] Leptosins C and F, isolated from the marine fungus Leptoshaeria sp., have inhibitory activity against topoisomerases I and II [77] (Scheme 2).…”

PARP and RIP 1 are required for autophagy induced by 11'-deoxyverticillin A, which precedes caspase-dependent apoptosis

“…27 It has been suggested that autophagy relates to apotosis by acting as a partner, an antagonist or an enabler of apoptosis depending on cell type, stimulus and environment. 28,29 11'-deoxyverticillin A, a natural product isolated from the Cordyceps-colonizing fungus Gliocladium sp., 30 is a member of a class of fungal secondary metabolites known as epipolythiodioxopiperazines (ETPs). 31 The ETPs have been previously reported to have a broad range of biological activities including antimicrobial, antiparasitic, antiviral, immunosuppressive and/ or anti-inflammatory effects.…”

Evaluación in vitro de diez cepas de hongos nematófagos para el control de Meloidogyne exigua, Meloidogyne incognita y Radopholus similis

“…De algunas cepas de G. roseum, se han aislado compuestos nematicidas [32] [33]. En el caso de G. butleri se conoce que produce una gran cantidad de quitosano, que se utiliza en agricultura como estimulante del crecimiento y la inmunidad, sin embargo las referencias a su capacidad nematicida son casi nulas [34].…”