Total Syntheses of (−)- and (+)-Goniomitine

Mizutani, Masaya; Inagaki, Fuyuhiko; Nakanishi, Takeo; Yanagihara, Chihiro; Tamai, Ikumi; Mukai, Chisato

doi:10.1021/ol200320z

Cited by 71 publications

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“…During our studies on the syntheses of various kind of alkaloids, [11][12][13][14][15][16][17][18][19] we became very interested in the highly conjugated and characteristic dimeric structure of scytonemin as well as its biological activity. We postulated that the origin of the biological activity of scytonemin (1) might be elucidated by comparison with its carbon analogue, in which two nitrogen atoms are replaced by two carbon atoms.…”

Section: )mentioning

confidence: 99%

“…[5][6][7][8] Besides this important function, scytonemin exhibits a biological activity as a small molecule inhibitor of polo-like kinase 1 9) and possesses anti-inflammatory and antiproliferative properties. 10) During our studies on the syntheses of various kind of alkaloids, [11][12][13][14][15][16][17][18][19] we became very interested in the highly conjugated and characteristic dimeric structure of scytonemin as well as its biological activity. We postulated that the origin of the biological activity of scytonemin (1) might be elucidated by comparison with its carbon analogue, in which two nitrogen atoms are replaced by two carbon atoms.…”

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Synthesis of a Carbon Analogue of Scytonemin

Mukai

Arima

Hirata

et al. 2015

CHEMICAL & PHARMACEUTICAL BULLETIN

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The synthesis of a carbon analogue of scytonemin was accomplished on the basis of molybdenummediated intramolecular double Pauson-Khand type reaction of bis(allenyne), followed by the double aldol condensation of the formed double Pauson-Khand type adduct.Key words scytonemin; allene; [2+2+1] cycloaddition; alkyne; molybdenum; aldol condensation Scytonemin (1) is the cyanobacterial dimeric alkaloid pigment, whose chemical structure has been elucidated by Gerwick and co-workers in 1993, 1) over 100 years after its discovery. Scytonemin has an intriguing novel structural feature, which consists of a two 1,1′-linked cyclopent [b] indole-2(1H)-one framework possessing 4-hydroxybenzylidenes at the 3-positions of the fused tricyclic systems. The biosynthetic studies of scytonemin have been recently made by Walsh and Balskus.2,3) In 2011, Mårtensson and colleagues achieved the first total synthesis of scytonemin by taking advantage of the tandem Heck carbocyclization/Suzuki-Miyaura coupling and a bioinspired oxidative dimerization. 4) Of particular interest is its interesting biological features. Scytonemin is a UVabsorbing pigment that protects important cellular components in a cyanobacteria against harmful UV radiation. [5][6][7][8] Besides this important function, scytonemin exhibits a biological activity as a small molecule inhibitor of polo-like kinase 1 9) and possesses anti-inflammatory and antiproliferative properties. 10)During our studies on the syntheses of various kind of alkaloids, [11][12][13][14][15][16][17][18][19] we became very interested in the highly conjugated and characteristic dimeric structure of scytonemin as well as its biological activity. We postulated that the origin of the biological activity of scytonemin (1) might be elucidated by comparison with its carbon analogue, in which two nitrogen atoms are replaced by two carbon atoms. Therefore, our endeavor was directed toward the synthesis of 2, a carbon analogue of scytonemin (1) (Chart 1).In 2005, Liu and Datta developed the efficient synthesis of 1H-cyclopent[a] inden-2-one (4a) from 1-ethynyl-2-(1,2-propadienyl) benzene (3a) through the Mo(CO) 3 (MeCN) 3 -mediated carbonylative [2+2+1] ring-closing reaction at 25°C in a stoichiometric manner 20) (Chart 2). They also reported the catalytic version of that transformation in the presence of 5 mol% of [RhCl(CO) 2 ] 2 at 90°C to furnish 4a in 62% yield along with the by-production of 2-methylnaphthalene (5), the latter of which should be arisen from the MyersSaito cycloaromatization 21-25) of 3a. We have independently reported that treatment of 3-(2-ethynylphenyl) prop-2-ynyl benzenesulfinate (6) with 2.5 mol% of [RhCl(CO) 2 ] 2 at 40°C in an atmosphere of CO effected the successive 2,3-sigmatropic rearrangement and carbonylative [2+2+1] ring-closing reaction of the resulting allenyne species 3b to afford the 8-(phenylsulfonyl)-1H-cyclopent[a] inden-2-one (4b) in a high yield.26) In this case, the formation of 2-methylnaphthalene could not be detected in the reaction mixture. We now report t...

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confidence: 99%

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confidence: 99%

Synthesis of a Carbon Analogue of Scytonemin

Mukai

Arima

Hirata

et al. 2015

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…Using the same strategy, but starting from (+)-ent-1092, the authors have synthesized 46 (53), to meta-chloroperbenzoic acid. The reaction proceeded probably through ring expansion in 1097 and afforded acetal 1098 (82%) as an epimeric mixture with 1098a predominating (3:1).…”

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“…Mukai and coworkers have described46 a synthesis of both racemic and optically active goniomitine, which features the authors' 2-vinylindole synthesis47 and alkene cross-metathesis as the important steps, Schemes 20 and 21. Synthesis of 2-vinylindole synthon 1084 commenced with the preparation from benzyloxyacetaldehyde of alkynol 1080 (84%) which was converted into mesylate 1081 and then reacted with tributylstannane in the presence of LDA and copper(I) bromide (Marshall's conditions) to give Collect.…”

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“…Saturation of the double bond in 1087 led to lactam 1088 (97%), the reduction of which with diisobutylaluminum hydride provided directly tetracycle 1089 (87%). Subsequent removal of the N-benzyl group by hydrogenolysis and O-desilylation (TBAF) completed the total synthesis of racemic goniomitine (1049).Synthesis of (-)-goniomitine (1049) started46 with the two-step preparation of vinyllactam (-)-1092 from known 48 allyllactam 1091 (66%), Scheme 21. Application of the above "neat" cross-metathesis procedure with 30 mole % Hoveyda-Grubbs 2nd generation catalyst to 1084 and lactam 1092 (3.5 eq) had failed, however, the reaction was conveniently Collect.…”

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Recent developments in syntheses of the post-secodine indole alkaloids. Part III: Rearranged alkaloid types

Hájíček¹

2011

Collect. Czech. Chem. Commun.

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The third part of a planned review on developments in the field of total and formal total synthesis of the post-secodine indole alkaloids focuses on types of rearranged alkaloids, i.e. on the skeletons with altered connectivities next to the indol(e)ine moiety, especially with a new bond to N-1. It reviews the synthesis of melodane, goniomitine, chippiine/dippinine, lirofoline and tronocarpine alkaloids, as well as alkaloids of secoschizozygane/vallesamidine, schizozygane and isoschizozygane type. It covers the literature from approximately 1991 up to May 2011. A review with 115 references.

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Alkene Cross‐Metathesis Reactions

et al. 2021

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This chapter describes olefin cross‐metathesis (CM) reactions catalyzed by ruthenium, molybdenum, and tungsten complexes and surveys the literature from 1993 through 2020. Cross‐metathesis has been applied to the synthesis of a wide range of functionalized alkenes, including natural and biologically active products. Due to its simplicity and inherit atom economy, CM has found applications in the preparation of fine chemicals and various building blocks, and in transformations of biomass. Tandem reactions involving CM as the key step are also reviewed. Examples discussed in this chapter serve to illustrate how the reactivity of alkene substrates in CM depends on the presence of functional groups and steric congestion in the proximity of the reacting double bonds. A discussion of the mechanism of olefin metathesis is also included.

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Total Syntheses of (−)- and (+)-Goniomitine

Cited by 71 publications

References 15 publications

Synthesis of a Carbon Analogue of Scytonemin

Synthesis of a Carbon Analogue of Scytonemin

Recent developments in syntheses of the post-secodine indole alkaloids. Part III: Rearranged alkaloid types

Alkene Cross‐Metathesis Reactions

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