251091-29-9Relevant academic research and scientific papers
Biomimetic explorations towards the bisorbicillinoids: Total synthesis of bisorbicillinol, bisorbibutenolide, and trichodimerol
Nicolaou,Simonsen, Klaus B.,Vassilikogiannakis, Georgios,Baran, Phil S.,Vidali, Veroniki P.,Pitsinos, Emmanuel N.,Couladouros, Elias A.
, p. 3555 - 3559 (1999)
Strikingly simple cascade dimerization sequences can be used to assemble the complex frameworks of bisorbicillinoids such as bisorbicillinol (1), bisorbibutenolide (2), and trichodimerol (3). The mechanistic facets of the biomimetic total syntheses of these bioactive natural products were also explored. Inspection of the unique molecular architecture of these compounds reveals that they are likely to be assembled in nature by a dimerization of two oxidized forms of sorbicillin.
A two-step total synthesis of the natural pentacycle trichodimerol, a novel inhibitor of TNF-α production
Barnes-Seeman, David,Corey
, p. 1503 - 1504 (1999)
(formula presented) Trichodimerol (1) can be synthesized by a remarkable dimerization of the chiral hydroxy dienone 5.
Stereoselective Total Synthesis of Bisorbicillinoid Natural Products by Enzymatic Oxidative Dearomatization/Dimerization
Sib, Anna,Gulder, Tobias A. M.
, p. 12888 - 12891 (2017/09/14)
Natural products are a virtually inexhaustible source of small molecules with spectacular molecular architectures and biomedical potential. Their structural complexity generates formidable challenges to total synthesis but often also precludes time- and resource-efficient, stereoselective synthetic access. Biosynthetically, nature frequently uses dimerization and oligomerization reactions to produce highly challenging frameworks from simple starting materials. Impressive examples are the bisorbicillinoids, a family of fungal natural products thought to originate from the polyketide precursor sorbicillin. Utilizing the recombinant oxidoreductase SorbC from the sorbicillin biosynthetic gene cluster, a robust, fully stereoselective synthesis of bisorbicillinoid natural products and unnatural side-chain analogues was developed.
Total synthesis and stereochemical assignment of (±)-sorbiterrin A
Qi, Chao,Qin, Tian,Suzuki, Daisuke,Porco, John A.
, p. 3374 - 3377 (2014/03/21)
A concise, biomimetic approach to sorbiterrin A has been developed employing consecutive Michael additions of a 4-hydroxypyrone to a sorbicillinol derivative and silver nanoparticle-mediated bridged aldol/dehydration to construct the [3.3.1] ring system. The relative stereochemistry of sorbiterrin A was unambiguously confirmed by X-ray crystallographic analysis.
Sorbicillinol, a key intermediate of bisorbicillinoid biosynthesis in Trichoderma sp. USF-2690.
Abe,Sugimoto,Arakawa,Tanji,Hirota
, p. 2271 - 2279 (2007/10/03)
In the course of our screening program for free radical scavengers from Trichoderma sp. USF-2690, we found an unidentified metabolite (1) that appeared by the method used for HPLC analysis. Metabolite 1 gradually decreased with the production of bisorbicillinoids and was easily missed during the general isolation procedure. The LC-ESI-MS (negative) analysis for 1 gave m/z 247 as the (M-1)- ion peak. The hydrolysis of synthetic 6-O-acetylsorbicillinol (+/- -2) by 0.05 M KOH and acetylation of product 1 in an aqueous solution indicated that the structure of 1 was (6S)-4-(2,4-hexadienoyl)-3,6-dihydroxy-2,6-dimethyl-2,4-cyclohexadien-1-one, designated sorbicillinol, a quinol that has been postulated to be important in bisorbicillinoid biosynthesis.
Biomimetic Total Synthesis of Bisorbicillinol, Bisorbibutenolide, Trichodimerol, and Designed Analogues of the Bisorbicillinoids
Nicolaou,Vassilikogiannakis, Georgios,Simonsen, Klaus B.,Baran, Phil S.,Zhong, Yong-Li,Vidali, Veroniki P.,Pitsinos, Emmanuel N.,Couladouros, Elias A.
, p. 3071 - 3079 (2007/10/03)
The bisorbicillinoids are a growing class of novel natural products endowed with unique biological activity and are associated with fascinating hypotheses for their biosynthesis. A full account of our biomimetic explorations toward the bisorbicillinoids including the total syntheses of bisorbicillinol (1), bisorbibutenolide (2), and trichodimerol (4) from sorbicillin (3) is disclosed. Utilizing the novel dimerization reactions discovered and fine-tuned en route to 1 and 4, several analogues of these natural products have been synthesized. Furthermore, studies on the scope of these novel cycloaddition reactions and the isolation of a number of unexpected products along with proposed mechanisms for their formation are reported. These findings add to our knowledge of the largely unexplored chemistry of o-quinols and related aromatic systems.
