Total synthesis of (−)-phaeosphaeride B by a biomimetic conversion from (−)-phaeosphaeride A

Kobayashi, Kenichi; Kunimura, Risako; Tanaka, Kosaku; Tamura, Osamu; Kogen, Hiroshi

doi:10.1016/j.tet.2017.03.020

Cited by 6 publications

(12 citation statements)

References 20 publications

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“…Our synthesis commenced with the preparation of the key synthetic intermediate 7 used to obtain phaeosphaerides A and B (Scheme 2). According to our previously reported protocol [11], n -hexanal was converted over 10 steps into aldehyde 6 , which was then subjected to the vinyl anion aldol reaction using sodium bis(trimethylsilyl)amide (NaHMDS) in THF. In our previous work, dihydropyran derivative 7 was obtained in 56% yield but the reaction unexpectedly suffered from low yield and lack of reproducibility.…”

Section: Resultsmentioning

confidence: 99%

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Total Synthesis of the Proposed Structure of Paraphaeosphaeride C

2019

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Paraphaeosphaeride C is a demethoxy derivative of phaeosphaeride A and exhibits STAT3 inhibitory activity. Our previous papers reported the total synthesis of phaeosphaeride A using a diastereoselective vinyl anion aldol reaction as the key step to construct the dihydropyran ring. In this work, the first total synthesis of the proposed structure of paraphaeosphaeride C was achieved via a similar synthetic strategy. The synthetic compound was characterized through extensive nuclear magnetic resonance (NMR) analysis but the 1H and 13C-NMR data for this compound did not correspond to those reported in the literature for paraphaeosphaeride C.

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Section: Resultsmentioning

confidence: 99%

“…In our previous work, we achieved the total synthesis of phaeosphaerides A ( 4 ) and B ( 5 ), using a diastereoselective vinyl anion aldol reaction of aldehyde 6 to form 7 as the key step for assembling the dihydropyran core (Scheme 1) [9,10,11].…”

Section: Introductionmentioning

confidence: 99%

Total Synthesis of the Proposed Structure of Paraphaeosphaeride C

2019

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“…After the successful total synthesis of (±)-phaeosphaeride B by Sarli, we demonstrated a biomimetic transformation from (−)-phaeosphaeride A to (−)-phaeosphaeride B [12]. We posited that phaeosphaerides A and B would be biosynthetically interconverted under acidic conditions.…”

Section: Scheme 6 Sarli's Total Synthesis Of (±)-Phaeosphaeride B (1b)mentioning

confidence: 94%

“…The correct structure of natural (−)-phaeosphaeride A was thus shown to be the enantiomer 1d of synthetic 1c [11]. Then, natural (−)-phaeosphaeride A was synthesized by using AD-mix-α instead of AD-mix-β in the first step (Scheme 5) [12]. shown to be the enantiomer 1d of synthetic 1c [11].…”

Section: Stereochemical Determination Of Natural (−)-Phaeosphaeride Amentioning

confidence: 99%

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Total Synthesis and Biological Evaluation of Phaeosphaerides

2018

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This article reviews studies regarding the total synthesis of phaeosphaerides A and B, nitrogen-containing bicyclic natural products isolated from an endophytic fungus. Numerous synthetic efforts and an X-ray crystal structure analysis of phaeosphaeride A have enabled revision of its originally proposed structure. In addition, a successful protic acid-mediated transformation of phaeosphaeride A to phaeosphaeride B revealed the hypothetical biosynthesis of phaeosphaeride B from phaeosphaeride A. Structure–activity relationship studies of phaeosphaeride derivatives are also discussed.

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