Highly efficient method for coriolin synthesis

Domon, Kei; Masuya, Keiichi; Tanino, Keiji; Kuwajima, Isao

doi:10.1016/s0040-4039(96)02328-3

Cited by 14 publications

(3 citation statements)

References 15 publications

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“…The wide range of applicability as well as the high selectivities of this transformation would have advantages for natural product synthesis. Indeed, we have already demonstrated the utility of the present methodology in total synthesis of coriolin, and synthetic studies on other natural products are now in progress.…”

Section: Discussionmentioning

confidence: 82%

Highly Regio- and Stereoselective [3+2] Cyclopentanone Annulation Using a 3-(Alkylthio)-2-siloxyallyl Cationic Species

et al. 1998

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A new synthetic method for functionalized cyclopentanones was developed on the basis of a [3+2] cycloaddition reaction of a 1-(methylthio)-2-siloxyallyl cationic species and olefins. Allyl acetates 1a and 1b, which are the precursors of the allyl cationic species, are easily prepared in three or four steps from commercially available compounds. Under the influence of EtAlCl2 or AlCl3, 1a or 1b reacted with various kinds of olefins such as enol ethers, vinyl sulfides, styrenes, and trialkylolefins to afford the corresponding cyclopentanones in good yields. It is noteworthy that the sterically more hindered regioisomer was predominantly formed in every case. Furthermore, the reactions of 1b with vinyl sulfides exhibited surprisingly high stereoselectivity, which can be rationalized by the six-membered transition state models involving an orbital interaction between the sulfur atom of the vinyl sulfide and the α-carbon of the allyl cation.

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Section: Discussionmentioning

confidence: 82%

Highly Regio- and Stereoselective [3+2] Cyclopentanone Annulation Using a 3-(Alkylthio)-2-siloxyallyl Cationic Species

et al. 1998

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“…148 A highly efficient method for the synthesis of coriolin has been developed. 149 The biosynthesis of the tremulane sesquiterpenes, in liquid cultures of the wood-rotting fungus Phelinus tremulae, has been studied using stable isotopes. 150 A new lactone with a lactarane skeleton, russulactarororufin 102, has been isolated from Russula brevipes.…”

Section: Caryophyllane Cyclocaryophyllane Modhephane Presilphiperfola...mentioning

confidence: 99%

Natural sesquiterpenoids

Fraga¹

1999

Nat. Prod. Rep.

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“…In the past decades, many elegant methods and strategies for constructing linear 5/5/5 structures have been developed. The strategies for these syntheses can be devided into three catalogs (using syntheses of hypnophilin and coriolin as examples): (1) Synthesizing three five-membered rings in proper sequences, [24][25][26][27][28][29][30][31][32][33] (2) synthesizing two or three five-membered rings by a cascade cyclization process in one step, [34][35][36][37][38] and (3) skeleton rearrangement. [39][40][41][42][43][44][45][46][47] Only a few of these reported strategies used transannular reactions (such as ene and aldol reactions) converting 5/8 bicycles, as precursors, to 5/5/5 ring systems (see examples from Pattenden, Wender, and List in Fig.…”

Section: Introductionmentioning

confidence: 99%

Syntheses of (+)-Antrodiellin B, (−)-Hypnophilin and (−)-Coriolin and Strained 5/5/5 and 5/6/4 Skeletons via [5+2+1]/Epoxidation/Transannular Radical Cyclization

Wang

Huang

2022

Preprint

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Nature produces many molecules (so-called natural products) containing compact scaffolds such as cis-anti-cis-configurated 5/5/5 and 5/6/4 tricycles. But other molecules with more strained structures, such as trans-anti-cis-configurated 5/5/5 tricycles have been rarely found in nature. Accessing all these natural and non-natural molecules will strengthen the power of organic synthesis and benefit many fields such as medicinal chemistry, chemical biology that are heavily dependent on the available quantity of new/important molecules. Herein, we report a new strategy to synthesize molecules with cis-anti-cis-configurated 5/5/5 tricycles, 5/6/4 tricycles and trans-anti-cis-configurated 5/5/5 tricyclic skeletons by [5+2+1]/epoxidation/transannular radical cyclization strategy, where challenging cis and trans 5/8 bicycles with both ene and carbonyl functional groups were accessed by Rh-catalyzed [5+2+1] reaction of ene-vinylcyclopropanes and carbon monoxide, followed by epoxidation of the double bond in the 5/8 bicycles, and Ti(III) mediated epoxide/carbonyl cyclization to build target skeletons. This strategy was further applied to the first total synthesis of (+)-antrodiellin B, the asymmetric total synthesis of (−)-hypnophilin and formal synthesis of (−)-coriolin with cis-anti-cis configurated 5/5/5 skeleton (both hypnophilin and coriolin are highly oxidized and have significant biological activities).

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Highly efficient method for coriolin synthesis

Cited by 14 publications

References 15 publications

Highly Regio- and Stereoselective [3+2] Cyclopentanone Annulation Using a 3-(Alkylthio)-2-siloxyallyl Cationic Species

Highly Regio- and Stereoselective [3+2] Cyclopentanone Annulation Using a 3-(Alkylthio)-2-siloxyallyl Cationic Species

Natural sesquiterpenoids

Syntheses of (+)-Antrodiellin B, (−)-Hypnophilin and (−)-Coriolin and Strained 5/5/5 and 5/6/4 Skeletons via [5+2+1]/Epoxidation/Transannular Radical Cyclization

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