A novel chiral route to substituted tetrahydrofurans.  Total synthesis of (+)-verrucosidin and formal synthesis of (-)-citreoviridin

Hatakeyama, Susumi; Sakurai, K.; Numata, Hirotoshi; Ochi, Noriko; Takano, Seiichi

doi:10.1021/ja00223a055

Cited by 52 publications

(21 citation statements)

References 4 publications

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“…Conversion into the corresponding lithium acetylides and reaction Scheme 3. Non-racemic epoxy alcohols from desymmetrizing epoxidations of divinylcarbinols reported earlier [4][5][6][7][8][9][10] or studied here.…”

Section: Preparation Of Disubstituted C S -Symmetrical Divinylcarbinolsmentioning

confidence: 69%

“…SAEs of symmetrically substituted penta-1,4-dien-3-ols 3 (R 1 and/or R 2 ¼ 6 H, "divinyl carbinols") proceed similarly. [6][7][8][9][10] The essence of these reactions is threefold: They provide monoepoxy alcohols 4 in preference to bisepoxides 5; they proceed with unusually high diastereoselectivities; they exhibit extraordinary enantiopurities (up to 99% ee). Scheme 2 reveals these features only implicitly.…”

Section: Introductionmentioning

confidence: 99%

“…[10] In addition, we are aware of three trans,trans-disubstituted divinylcarbinols which were subjected to desymmetrizing SAEs (!anti-9, [7] anti-10, [8] anti-11 [6a,b,9] ). For monoepoxide anti-11 once more, an inverse proportionality between ee and time was published [93% ee (after 1 h)!…”

Section: Introductionmentioning

confidence: 99%

“…SAE of achiral secondary allyl alcohols ("divinylcarbinols"). [4][5][6][7][8][9][10] DET = diethyl tartrate, DiPT = diisopropyl tartrate.…”

Section: Introductionmentioning

confidence: 99%

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Stereocomplementary Desymmetrizations of Divinylcarbinols by Zirconium(IV)‐ vs. Titanium(IV)‐Mediated Asymmetric Epoxidations

2008

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Substituted C s -symmetric penta-1,4-dien-3-ols ("divinylcarbinols") containing cis-or trans-disubstituted C=C bonds were desymmetrized by asymmetric monoepoxidations. Sharpless conditions gave anti-configured monoepoxides. For cis,cis-divinylcarbinols this was unprecedented. Oxidation with tert-butyl hydroperoxide (t-BuOOH) in the presence of zirconium tetraisopropoxide [ZrA C H T U N G T R E N N U N G (O-iPr) 4 ] and a dialkyl tartrate led to the corresponding syn-configured monoepoxides. Under the reaction conditions the ee of monoepoxide syn-12 increased with time from 75 to 99% ee. The reason is the preferential overoxidation of its minor enantiomer. The ease of preparation and multitude of functional groups make epoxides 12-14 worthwhile building blocks for the synthesis of non-racemic structures.

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Section: Preparation Of Disubstituted C S -Symmetrical Divinylcarbinolsmentioning

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…SAE of achiral secondary allyl alcohols ("divinylcarbinols"). [4][5][6][7][8][9][10] DET = diethyl tartrate, DiPT = diisopropyl tartrate.…”

Section: Introductionmentioning

confidence: 99%

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Stereocomplementary Desymmetrizations of Divinylcarbinols by Zirconium(IV)‐ vs. Titanium(IV)‐Mediated Asymmetric Epoxidations

2008

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“…Our basic idea to access compound 43 began with asymmetric epoxidation 62,63) of σ-symmetrical dialkenylcarbinol 47 and then the sequence proceeded through Mitsunobu inversion, introduction of a nitrogen atom by taking advantage of the epoxy alcohol functionality, construction of a Z-unsatuChart 12. Second-Generation Synthesis of Dysiherbaine Chart 13.…”

Section: Total Synthesis Of Dysiherbainementioning

confidence: 99%

Total Synthesis of Biologically Active Natural Products Based on Highly Selective Synthetic Methodologies

Hatakeyama

2014

CHEMICAL & PHARMACEUTICAL BULLETIN

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Total syntheses of structurally and biologically intriguing natural products relying on new synthetic methodologies are described. This article features cinchona alkaloid-catalyzed asymmetric Morita-BaylisHillman reactions, heterocycle syntheses based on rhodium-catalyzed C-H amination and indium-catalyzed Conia-ene reactions, and their utilization for the syntheses of the phoslactomycin family of antibiotics, glutamate receptor agonists and antagonists, and alkaloids with characteristic highly substituted pyrrolidinone core structures.

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Manganese‐Catalyzed Chemoselective Direct Hydrogenation of α,β‐Epoxy Ketones and α‐Ketoamides at Room Temperature

Shabade,

Singh,

Gonnade

et al. 2024

Adv Synth Catal

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Chemoselective hydrogenation of α,β‐epoxy ketones and α‐ketoamides is achieved at room temperature (25 °C) using 2.0 bar H2 and a pincer‐ligated Mn(I) catalyst that provides synthetically valuable α‐hydroxy epoxides and α‐hydroxy amides. This protocol applies to a wide range of alkyl and aryl‐substituted α,β‐epoxy ketones, including terpenes (α‐ionone, nootkatone, and R‐carvone)‐ and steroids (testosterone and progesterone)‐derived epoxy ketones, and tolerates H2 sensitive functionalities, such as halides, acetyl, nitrile, nitro, epoxide, alkenyl and alkynyl groups. Additionally, the α‐ketoamides bearing reducible functional groups, including acetyl and diazo benzene, were untouched under this protocol and selectively converted to α‐hydroxy amides. A preliminary mechanistic study highlighted the metal‐ligand cooperative H2 activation process.

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A novel chiral route to substituted tetrahydrofurans. Total synthesis of (+)-verrucosidin and formal synthesis of (-)-citreoviridin

Cited by 52 publications

References 4 publications

Stereocomplementary Desymmetrizations of Divinylcarbinols by Zirconium(IV)‐ vs. Titanium(IV)‐Mediated Asymmetric Epoxidations

Stereocomplementary Desymmetrizations of Divinylcarbinols by Zirconium(IV)‐ vs. Titanium(IV)‐Mediated Asymmetric Epoxidations

Total Synthesis of Biologically Active Natural Products Based on Highly Selective Synthetic Methodologies

Manganese‐Catalyzed Chemoselective Direct Hydrogenation of α,β‐Epoxy Ketones and α‐Ketoamides at Room Temperature

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