Relative reactivity of hydroxyl groups in inositol derivatives: role of metal ion chelation

Devaraj, Subramanian; Jagdhane, Rajendra C.; Shashidhar, Mysore S.

doi:10.1016/j.carres.2009.04.007

Cited by 11 publications

(7 citation statements)

References 65 publications

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“…The six secondary hydroxyl groups of myo -inositol possess similar reactivity . However, the reactivity of free cyclitol hydroxyls differs depending on several factors including ring conformation, hydrogen-bonding interactions with neighboring groups, and the conditions used for protection. , A commonly used strategy is acid-mediated ketalization of vicinal-diol groups. , Diketal (±)-1,2:4,5-di- O -isopropylidene- myo -inositol (Scheme , 21 ) can be synthesized from myo -inositol by a simple two-step process. , The 1,2:4,5-diketal structure forces the ring into a rigid conformation, facilitating selective individual protection of the other two free hydroxyls as a 6- O -PMB derivative and 3- O -triflate for activation. This conformational rigidity stabilizes the triflate from undergoing β-elimination under alkaline conditions .…”

Section: Resultsmentioning

confidence: 99%

“…Compound 35, the less polar product on TLC (50% EtOAc/petroleum ether), was obtained as a clear oil, which turned into a waxy solid (140 mg, 57%). 1 H NMR (400 MHz, CD 3 COCD 3 ) δ 7.17 6 (38). The title compounds were prepared from 32 using the same method as that for 35 and 36.…”

Section: ■ Conclusionmentioning

confidence: 99%

“…37 However, the reactivity of free cyclitol hydroxyls differs depending on several factors including ring conformation, hydrogen-bonding interactions with neighboring groups, and the conditions used for protection. 4,38 A commonly used strategy is acid-mediated ketalization of vicinal-diol groups. 37,39 Diketal (±)-1,2:4,5-di-O-isopropylidene-myo-inositol (Scheme 1, 21) can be synthesized from myo-inositol by a simple two-step process.…”

Section: ■ Introductionmentioning

confidence: 99%

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Inositol Adenophostin: Convergent Synthesis of a Potent Agonist of d-myo-Inositol 1,4,5-Trisphosphate Receptors

Döhle

Mills

et al. 2020

ACS Omega

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d-myo-Inositol 1,4,5-trisphosphate receptors (IP3Rs) are Ca2+ channels activated by the intracellular messenger inositol 1,4,5-trisphosphate (IP3, 1). The glyconucleotide adenophostin A (AdA, 2) is a potent agonist of IP3Rs. A recent synthesis of d-chiro-inositol adenophostin (InsAdA, 5) employed suitably protected chiral building blocks and replaced the d-glucose core by d-chiro-inositol. An alternative approach to fully chiral material is now reported using intrinsic sugar chirality to avoid early isomer resolution, involving the coupling of a protected and activated racemic myo-inositol derivative to a d-ribose derivative. Diastereoisomer separation was achieved after trans-isopropylidene group removal and the absolute ribose–inositol conjugate stereochemistry assigned with reference to the earlier synthesis. Optimization of stannylene-mediated regiospecific benzylation was explored using the model 1,2-O-isopropylidene-3,6-di-O-benzyl-myo-inositol and conditions successfully transferred to one conjugate diastereoisomer with 3:1 selectivity. However, only roughly 1:1 regiospecificity was achieved on the required diastereoisomer. The conjugate regioisomers of benzyl derivatives 39 and 40 were successfully separated and 39 was transformed subsequently to InsAdA after amination, pan-phosphorylation, and deprotection. InsAdA from this synthetic route bound with greater affinity than AdA to IP3R1 and was more potent in releasing Ca2+ from intracellular stores through IP3Rs. It is the most potent full agonist of IP3R1 known and .equipotent with material from the fully chiral synthetic route.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Conclusionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Inositol Adenophostin: Convergent Synthesis of a Potent Agonist of d-myo-Inositol 1,4,5-Trisphosphate Receptors

Döhle

Mills

et al. 2020

ACS Omega

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“…We employed this compound as a diol‐type monomer for polyaddition with diisocyanates, leading to the successful synthesis of polyurethanes with high glass transition temperatures ( T g s) . Another functionalization method used frequently so far is orthoesterification, which allows protection of three hydroxyl groups of myo ‐inositol in one step . The product is a triol bearing a cyclic orthoester moiety, an oxygen‐containing analogue of adamantane.…”

Section: Introductionmentioning

confidence: 99%

Rigid triol and diol with adamantane-like core derived from naturally occurringmyo-inositol and their polyaddition with diisocyanates

Okamoto

Onoue

Kobayashi

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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Two orthoester derivatives 1 and 2 that are easily accessible from naturally occurring myo-inositol were exploited as new triol-and diol-type monomers bearing a rigid adamantane-like structure to polyaddition with diisocyanates that gave the corresponding networked and linear polyurethanes. DSC analysis of the networked polyurethanes revealed their high glass transition temperatures ranging from 155 to 248 C, suggesting the contribution of the rigidity of the adamantane-like structure introduced at the nodes of the networked polyurethanes 6. Besides, the polyaddition of 2 with diisocyanates gave the corresponding linear polyurethanes 4, of which glass transition temperatures were high, ranging from 105 to 177 C, presumably by virtue of the rigidity of the adamantane-like structure introduced into the main chains. T g s of the networked polyurethanes 6 were higher than those of the linear polyurethanes 4.

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“…[5][6][7][8] We had to prepare, store and use relatively larger amounts of 4 as a part of an ongoing program on the chemistry of inositols. 9 We were intrigued to realize that 4 was stable when stored as a solution in common organic solvents, but did not stay pure when stored as a gum at ambient temperature. A survey of the literature revealed that, while the physical state of 4 at ambient conditions was mentioned as a gum in some reports, 10,11 most others did not mention the physical state (or the purity) of the sample used for further synthetic transformations.…”

Section: Introductionmentioning

confidence: 99%

Achieving molecular stability of racemic 4-O-benzyl-myo-inositol-1,3,5-orthoformate through crystal formation

Sardessai

Shashidhar

2012

CrystEngComm

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Relative reactivity of hydroxyl groups in inositol derivatives: role of metal ion chelation

Cited by 11 publications

References 65 publications

Inositol Adenophostin: Convergent Synthesis of a Potent Agonist of d-myo-Inositol 1,4,5-Trisphosphate Receptors

Inositol Adenophostin: Convergent Synthesis of a Potent Agonist of d-myo-Inositol 1,4,5-Trisphosphate Receptors

Rigid triol and diol with adamantane-like core derived from naturally occurringmyo-inositol and their polyaddition with diisocyanates

Achieving molecular stability of racemic 4-O-benzyl-myo-inositol-1,3,5-orthoformate through crystal formation

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