Sorbicillinol, a Key Intermediate of Bisorbicillinoid Biosynthesis in Trichoderma sp. USF-2690

Novel Sorbicillin Derivatives with an Unprecedented Carbon Skeleton from the Sponge‐Derived Fungus Trichoderma Species

“…Our proposal is similar to that of Trifonov et al for the bisvertinols concerning the first steps of biosynthesis up to the formation of 10: [12] In their concept all known sorbicillinoid structures derive from 2,4-dimethyldodecyl units yielding sorbicillin, an assumption confirmed by Abe et al via biosynthetic studies with labeled acetate units. [24] According to Trifonov et al sorbicillin undergoes an epoxidation, a process also proposed as a key step in the biosynthesis of penicillic acid from orsellinic acid. [25] Opening of the epoxide ring would then lead to the quinol sorbicillinol (10).…”

Secondary metabolites from species of the biocontrol agent Trichoderma

“…22) have been isolated from a marine-derived fungus Penicillium species. Their structures were established on the basis of spectroscopic methods and their cytotoxic effects on P388 and A-549 cell lines were preliminarily examined (Liu et al 2005b) Several studies were performed in order to clarify the biosynthetic origin of this class of compounds (Abe et al 2001(Abe et al , 2002a. In support of the proposed biosynthetic pathways, two research groups independently and concurrently completed the total biomimetic syntheses of bisorbicillinol (138) and trichodimerol (135) (Fig.…”

Oxidative Dearomatization of Phenols: Why, How and What For?

“…These so-called ortho-quinols constitute the main structural element of the architecture of many natural products such as humulone (86) and its congeners, 92,93 wasabidienones 87/88 94,95 and related fungal metabolites such as aspersitin (89), 96 as well as the polyketide sorbicillinol (90) Several other natural products feature bicyclo[2.2.2]octane systems that can be synthetically derived from the Diels-Alder cyclodimerization of ortho-quinols. The bis(monoterpene) biscarvacrol (92), 101 the shikimate-derived grandifloracin (93), 102 the bis(sesquiterpenes) aquaticol (94) 103 and bacchopetiolone (95), 104 the polyketide bisorbicillinol (96), 105 the bis(diterpene) maytenone (97) 106 and the bis(dinorditerpene) hugonone A (98), 107 shown in Figure 6, are just a few illustrative examples of these natural products, whose retrosynthetic analysis at once reveals an ortho-quinol route for their construction. It is then obviously tempting to propose that these natural products are biosynthetically derived from ortho-quinol intermediates, themselves generated by some enzymatic hydroxylative dearomatization of phenolic precursors.…”