The biosynthesis of bisorbicillinoids: evidence for a biosynthetic route from bisorbicillinol to bisorbibutenolide and bisorbicillinolide

Abe, Naoki; Yamamoto, Kazunobu; Arakawa, Tadaharu; Hirota, Akira

doi:10.1039/b007181l

“…In addition, the PKS gene cluster containing SorbA, SorbB and SorbC has been characterized for sorbicillin (5) biosynthesis, and sorbicillinol (1) was proved as a key intermediate [11]. The extensive 13 C enrichment studies carried out by Abe and co-workers have unequivocally demonstrated that many of biosynthetic hypotheses of sorbicillinoids are correct [14][15][16][17]. There are still some uncertainties.…”

Section: Discussionmentioning

confidence: 99%

“…The biosynthesis studies of sorbicillinoids have been carried out [11,[14][15][16][17] and well summarized [1]. Sorbicillinol (1) has been hypothesized as a precursor of most sorbicillinoids that were biosynthesized by polyketide synthases (PKs) [14].…”

Section: Discussionmentioning

confidence: 99%

“…According to the structural features, sorbicillinoids can be divided into four groups: monomeric sorbicillinoids, bisorbicillinoids, trisorbicillinoids, and hybrid sorbicillinoids. Biosynthesis and chemical synthesis have been extensively studied and reviewed [1,11,[14][15][16][17]. In this mini-review, we focus on the occurrence and biological activities of sorbicillinoids, and 28 additional sorbicillinoids were added on the basis of the previous review [1].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Sorbicillinoids from Fungi and Their Bioactivities

Meng

¹

,

Wang

²

,

Xu

³

et al. 2016

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Sorbicillinoids are important hexaketide metabolites derived from fungi. They have a variety of biological activities including cytotoxic, antioxidant, antiviral and antimicrobial activity. The unique structural features of the sorbicillinoids make them attractive candidates for developing new pharmaceutical and agrochemical agents. About 90 sorbicillinoids have been reported in the past few decades. This mini-review aims to briefly summarize their occurrence, structures, and biological activities.

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“…Sorbicillin ( 1 a ) was first isolated from Penicillium notatum by Cram and Tishler in 1948 . 1 a is oxidatively dearomatised to form sorbicillinol ( 2 a ; Scheme A), which reacts with itself and other compounds to form various sorbicillinoids (Scheme ), more than 90 of which are known . Trifonov first proposed 2 a as the intermediate for self‐dimerization due to its dual diene and dienophile character .…”

Section: Introductionmentioning

confidence: 99%

Diels–Alder Reactions During the Biosynthesis of Sorbicillinoids

Kahlert

¹

,

Bassiony

²

,

Cox

³

et al. 2020

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The sorbicillinoids are a class of biologically active and structurally diverse fungal polyketides arising from sorbicillin. Through co‐expression of sorA, sorB, sorC, and sorD from Trichoderma reesei QM6a, the biosynthetic pathway to epoxysorbicillinol and dimeric sorbicillinoids, which resemble Diels–Alder‐like and Michael‐addition‐like products, was reconstituted in Aspergillus oryzae NSAR1. Expression and feeding experiments demonstrated the crucial requirement of the flavin‐dependent monooxygenase SorD for the formation of dimeric sorbicillinoids, hybrid sorbicillinoids, and epoxysorbicillinol in vivo. In contrast to prior reports, SorD catalyses neither the oxidation of 2′,3′‐dihydrosorbicillin to sorbicillin nor the oxidation of sorbicillinol to oxosorbicillinol. This is the first report that both the intermolecular Diels–Alder and Michael dimerization reactions, as well as the epoxidation of sorbicillinol are catalysed in vivo by SorD.

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“…[7,8] 1a is oxidatively dearomatised to form sorbicillinol (2a;S cheme 1A), [9] which reacts with itself and other compounds to form various sorbicillinoids (Scheme 1), more than 90 of which are known. [10][11][12] Tr ifonov first proposed 2a as the intermediate for self-dimerization due to its dual diene and dienophile character. [2,13,14] This was confirmed by Abe et al through elegant feeding experiments.…”

Section: Introductionmentioning

confidence: 99%

Diels–Alder Reactions During the Biosynthesis of Sorbicillinoids

Kahlert

¹

,

Bassiony

²

,

Cox

³

et al. 2020

View full text Add to dashboard Cite

The sorbicillinoids are a class of biologically active and structurally diverse fungal polyketides arising from sorbicillin. Through co‐expression of sorA, sorB, sorC, and sorD from Trichoderma reesei QM6a, the biosynthetic pathway to epoxysorbicillinol and dimeric sorbicillinoids, which resemble Diels–Alder‐like and Michael‐addition‐like products, was reconstituted in Aspergillus oryzae NSAR1. Expression and feeding experiments demonstrated the crucial requirement of the flavin‐dependent monooxygenase SorD for the formation of dimeric sorbicillinoids, hybrid sorbicillinoids, and epoxysorbicillinol in vivo. In contrast to prior reports, SorD catalyses neither the oxidation of 2′,3′‐dihydrosorbicillin to sorbicillin nor the oxidation of sorbicillinol to oxosorbicillinol. This is the first report that both the intermolecular Diels–Alder and Michael dimerization reactions, as well as the epoxidation of sorbicillinol are catalysed in vivo by SorD.

show abstract

The biosynthesis of bisorbicillinoids: evidence for a biosynthetic route from bisorbicillinol to bisorbibutenolide and bisorbicillinolide

Cited by 15 publications

References 14 publications

Sorbicillinoids from Fungi and Their Bioactivities

Sorbicillinoids from Fungi and Their Bioactivities

Diels–Alder Reactions During the Biosynthesis of Sorbicillinoids

Diels–Alder Reactions During the Biosynthesis of Sorbicillinoids

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