Enantiodivergent syntheses of (−)- and (+)-dysibetaine CPa and N-desmethyl analog

Sakai, Mariko; Tanaka, Kento; Takamizawa, Satoshi; Oikawa, Masato

doi:10.1016/j.tet.2014.05.053

Cited by 9 publications

(3 citation statements)

References 23 publications

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“…To illustrate the utility of our enantioselective cyclization of α,β-unsaturated carbonyl diazoacetates, we prepared key intermediates in the reported synthesis of DCG-IV and dysibetaine CPa from the cyclopropane-fused γ-lactone 2a (Scheme ). DCG-IV is a (dicarboxycyclopropyl)glycine that is known to be an anticonvulsant agent, being a potent group II mGluR agonist with neuroprotective properties, and is also active as an agonist at the NMDA receptor.…”

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confidence: 99%

Ru(II)–Pheox-Catalyzed Asymmetric Intramolecular Cyclopropanation of Electron-Deficient Olefins

et al. 2015

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The first highly enantioselective intramolecular cyclopropanation of electron-deficient olefins, in the presence of Ru(II)--Pheox catalyst, is reported. The corresponding cyclopropane-fused γ-lactones were obtained in high yields (up to 99%) with excellent enantioselectivities (ee up to 99%). Moreover, this method enables efficient access to enantioenriched dicarbonyl cyclopropane derivatives, which are important intermediates for the synthesis of various bioactive compounds.

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confidence: 99%

Ru(II)–Pheox-Catalyzed Asymmetric Intramolecular Cyclopropanation of Electron-Deficient Olefins

et al. 2015

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“…The organocatalytic asymmetric desymmetrization (ASD) of meso or achiral cyclic anhydrides with methanol introduces chirality into inexpensive achiral feedstock − and has been applied in the total synthesis of biologically active compounds. − A variety of effective organocatalysts have been developed for this ASD reaction, but those based on cinchona alkaloids are the most frequently used. In addition to the native alkaloids, several ether and 9-amino(9-deoxo) epi derivatives have been studied.…”

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confidence: 99%

A Theoretical Mechanistic Study of the Asymmetric Desymmetrization of a Cyclicmeso-Anhydride by a Bifunctional Quinine Sulfonamide Organocatalyst

et al. 2017

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Cinchona alkaloids and their derivatives are widely used as organocatalysts in asymmetric synthesis. In particular, sulfonamide derivatives of cinchona alkaloids are highly enantioselective desymmetrization catalysts in the ring opening of a variety of cyclic anhydrides. To better understand the mechanism of catalysis, as well as to identify the basis for enantioselectivity by this catalyst, we have performed DFT calculations of this reaction with a cyclic meso anhydride. Herein, we report calculations for two reaction pathways, one concerted and one stepwise, for the production of each enantiomer of the desymmetrized product using the complete sulfonamide catalyst I. Our results are consistent with both the enantioselectivity of this transformation and the catalytic role of the quinuclidine moiety. We find that the stepwise pathway is the relevant pathway in the production of the major enantiomer. Our calculations highlight the role of differential distortion of the anhydride-methanol complex in the transition state as the factor leading to stereoselectivity.

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“…We have been also interested in the synthesis of the neuronally active compounds, by the divergent route amenable to the structural analogs to discover novel compounds (Chiba et al 2015 ; Juknaitė et al 2013 ; Oikawa et al 2013 ; Sakai et al 2014 ; Sugeno et al 2014 ; Tanaka et al 2015 ). Here, we report our synthetic study using lipase-mediated esterification of prochiral acyclic 1,3-diol as the key step.…”

Section: Introductionmentioning

confidence: 99%

Studies on lipase-catalyzed asymmetric synthesis of (S)-(hydroxymethyl)glutamic acid (HMG)

Yoshioka

Oikawa

2015

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(S)-(Hydroxymethyl)glutamic acid was successfully synthesized in total 12 % yield over eight steps from tris(hydroxymethyl)aminomethane hydrochloride (Tris·HCl), employing lipase TL-induced enantioselective acetylation of a prochiral 1,3-diol as the key step.Electronic supplementary materialThe online version of this article (doi:10.1186/s40064-015-1503-8) contains supplementary material, which is available to authorized users.

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Enantiodivergent syntheses of (−)- and (+)-dysibetaine CPa and N-desmethyl analog

Cited by 9 publications

References 23 publications

Ru(II)–Pheox-Catalyzed Asymmetric Intramolecular Cyclopropanation of Electron-Deficient Olefins

Ru(II)–Pheox-Catalyzed Asymmetric Intramolecular Cyclopropanation of Electron-Deficient Olefins

A Theoretical Mechanistic Study of the Asymmetric Desymmetrization of a Cyclicmeso-Anhydride by a Bifunctional Quinine Sulfonamide Organocatalyst

Studies on lipase-catalyzed asymmetric synthesis of (S)-(hydroxymethyl)glutamic acid (HMG)

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