Flexible Stereo‐ and Regioselective Synthesis of <i>myo</i>‐Inositol Phosphates(Part 2): Via Nonsymmetrical Conduritol B Derivatives

Podeschwa, Michael; Plettenburg, Oliver; Altenbach, Hans‐Josef

doi:10.1002/ejoc.200400918

Cited by 14 publications

(7 citation statements)

References 45 publications

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“…We also prepared D ‐6‐ O ‐ and D ‐4‐ O ‐benzyl‐ myo ‐inositols 14 and ent ‐ 14 , which are precursors for the preparation of enantiomeric myo ‐inositol‐1,2,3,4,5‐pentakisphosphates. The benzyl ethers 14 and ent ‐ 14 have earlier been prepared from myo ‐inositol29 as well as from benzoquinone 30. The overall yield of enantiomeric benzyl ethers 14 and ent ‐ 14 in these reported procedures is in the range of 3–17 %.…”

Section: Resultsmentioning

confidence: 99%

Enhancing Intermolecular Benzoyl‐Transfer Reactivity in Crystals by Growing a “Reactive” Metastable Polymorph by Using a Chiral Additive

Murali

Shashidhar

Gonnade

et al. 2008

Chemistry A European J

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Racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoacetate, which normally crystallizes in a monoclinic form (form I, space group P2(1)/n) could be persuaded to crystallize out as a metastable polymorph (form II, space group C2/c) by using a small amount of either D- or L- 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoformate as an additive in the crystallization medium. The structurally similar enantiomeric additive was chosen by the scrutiny of previous experimental results on the crystallization of racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoacetate. Form II crystals can be thermally transformed to form I crystals at about 145 degrees C. The relative organization of the molecules in these dimorphs vary slightly in terms of the helical assembly of molecules, that is, electrophile (El)...nucleophile (Nu) and C-H...pi interactions, but these minor variations have a profound effect on the facility and specificity of benzoyl-group-transfer reactivity in the two crystal forms. While form II crystals undergo a clean intermolecular benzoyl-group-transfer reaction, form I crystals are less reactive and undergo non-specific benzoyl-group transfer leading to a mixture of products. The role played by the additive in fine-tuning small changes that are required in the molecular packing opens up the possibility of creating new polymorphs that show varied physical and chemical properties. Crystals of D-2,6-di-O-benzoyl-myo-inositol-1,3,5-orthoformate (additive) did not show facile benzoyl-group-transfer reactivity (in contrast to the corresponding racemic compound) due to the lack of proper juxtaposition and assembly of molecules.

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Section: Resultsmentioning

confidence: 99%

Enhancing Intermolecular Benzoyl‐Transfer Reactivity in Crystals by Growing a “Reactive” Metastable Polymorph by Using a Chiral Additive

Murali

Shashidhar

Gonnade

et al. 2008

Chemistry A European J

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“…The fractions containing product were concentrated and lyophilized to afford the pentakisphosphate 57 (44 mg, 98%) as a white fluffy solid. [α] 26 D −6.3 ( c 0.43, H 2 O, pH 10.2) [lit . [α] 20 D −6.2 ( c 1.29, H 2 O, pH 6)].…”

Section: Methodsmentioning

confidence: 99%

“…The Journal of Organic Chemistry in this paper, was verified by 31 P NMR (see the Supporting Information).…”

Section: Scheme 1 Structure Confirmation By Chemical Correlationmentioning

confidence: 99%

“…2,4-Di-O-benzyl-D-myo-inositol-1,3,5-orthoformate 6-Dibenzylphosphate (31) D-myo-Inositol-6-monophosphate Disodium Salt (32). To a solution of compound 31 (100 mg, 0.16 mmol) in MeOH (5 mL) was added 10% Pd/C (50 mg).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…13 C NMR (150 MHz, D 2 O): δ 78.0 (CH), 75.9 (CH), 75.4 (CH), 73.4 (CH), 72.6 (CH), 71.4 (CH). 31 D-myo-Inositol-3,4,5-trisphosphate Hexasodium Salt (43). To a solution of compound 42 (100 mg, 0.07 mmol) in MeOH (5 mL) was added 10% Pd/C (100 mg).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Yb(OTf)₃-Catalyzed Desymmetrization of myo-Inositol 1,3,5-Orthoformate and Its Application in the Synthesis of Chiral Inositol Phosphates

et al. 2017

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A variety of inositol phosphates including myo-inositol 1,4,5-trisphosphate, which is a secondary messenger in transmembrane signaling, were selectively synthesized via Yb(OTf)-catalyzed desymmetrization of myo-inositol 1,3,5-orthoformate using a proline-based chiral anhydride as an acylation precursor. The investigated catalytic system could regioselectively differentiate the enantiotopic hydroxy groups of myo-inositol 1,3,5-orthoformate in the presence of a chiral auxiliary. This key step to generate a suitably protected chiral myo-inositol derivatives is described here as a unified approach to access inositol phosphates.

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Photokatalytische aerobe Phosphatierung von Alkenen

et al. 2018

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Es wurde ein katalytisches Verfahren fürdie direkte Phosphatierung einfacher unpolarisierter Alkene entwickelt, das erstmals die Nutzung von gewçhnlichen unaktivierten Phosphorsäurediestern als Phosphatquelle und O 2 als terminales Oxidationmittel ermçglicht. Die Methode erlaubt einen direkten und hçchst çkonomischen Aufbau von verschiedenen Allylphosphatestern. Im Vergleichz uh erkçmmlichen Verfahren zur Gewinnung von Phosphorsäureestern ist die aerobe Phosphatierung vollständig komplementär, da erstere zum Großteil auf der Verwendung von vorfunktionalisierten oder voraktivierten Reagenzien wie Alkoholen oder Phosphorylhalogeniden beruhen. Ermçglicht wird die Reaktion durchdas katalytische Zusammenwirken eines Photokatalysators und einer Selen-p-Säure über eine Abfolge von Ein-Elektronen-Transferprozessen. Tabelle 4: Redox-Alkylierung von Alkenen durch sequenzielle aerobe Phosphatierung und nukleophile Substitution [a][a] Ausbeutenb eziehen sich auf reine, isolierte Verbindungen.

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Flexible Stereo‐ and Regioselective Synthesis of myo‐Inositol Phosphates(Part 2): Via Nonsymmetrical Conduritol B Derivatives

Cited by 14 publications

References 45 publications

Enhancing Intermolecular Benzoyl‐Transfer Reactivity in Crystals by Growing a “Reactive” Metastable Polymorph by Using a Chiral Additive

Enhancing Intermolecular Benzoyl‐Transfer Reactivity in Crystals by Growing a “Reactive” Metastable Polymorph by Using a Chiral Additive

Yb(OTf)₃-Catalyzed Desymmetrization of myo-Inositol 1,3,5-Orthoformate and Its Application in the Synthesis of Chiral Inositol Phosphates

Photokatalytische aerobe Phosphatierung von Alkenen

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Flexible Stereo‐ and Regioselective Synthesis of myo‐Inositol Phosphates(Part 2): Via Nonsymmetrical Conduritol B Derivatives

Cited by 14 publications

References 45 publications

Enhancing Intermolecular Benzoyl‐Transfer Reactivity in Crystals by Growing a “Reactive” Metastable Polymorph by Using a Chiral Additive

Enhancing Intermolecular Benzoyl‐Transfer Reactivity in Crystals by Growing a “Reactive” Metastable Polymorph by Using a Chiral Additive

Yb(OTf)3-Catalyzed Desymmetrization of myo-Inositol 1,3,5-Orthoformate and Its Application in the Synthesis of Chiral Inositol Phosphates

Photokatalytische aerobe Phosphatierung von Alkenen

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Yb(OTf)₃-Catalyzed Desymmetrization of myo-Inositol 1,3,5-Orthoformate and Its Application in the Synthesis of Chiral Inositol Phosphates