A Short and Efficient Route from myo- to neo-Inositol

Wessig, Pablo; Möllnitz, Kristian; Hübner, Sebastian

doi:10.1055/s-0029-1220071

Cited by 12 publications

(3 citation statements)

References 17 publications

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“…Some methods for the preparation of neo-inositol or its derivatives were reported but none of them were feasible [4]. We therefore developed anew efficient method for the preparation of neofrom myo-inositol [5]. The crystal structure of the title compound unequivocally proves the correct stereochemistry of the product.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of 1r,2c,3c,4t,5t,6t-1,2,3,4,5,6-hexakistrimethylsilanyloxy- cyclohexane, C24H60O6Si6

Wessig¹,

Möllnitz²,

Kelling³

et al. 2011

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialThe title compound was synthesized by treating neo-inositol with trimethylsilyl chloride in triethylamine. Colorless crystals where obtained by slow volatilizing CDCl 3 from an NMR sample. Experimental detailsThe hydrogen atoms were calculated in their expected positions and included in the refinement as riding atoms. The U iso (H) values were constrained to be 1.2 U eq (CH) and 1.5 U eq (CH 3 ), respectively. In one of both molecules two methyl groups of one silanyloxy substituent are disordered over two sides with an occupation ratio of 0.5/0.5. The terminal methyl groups display enhanced librational motions, which is caused by rotation around the silicon-oxygen bond. DiscussionIn connection with our investigations concerning new molecular rods with ketal moeties as key structural element [1-3] we were interested in six-membered saturated rings bearing four hydroxyl groups with the stereochemical pattern 1r,2c,4t,5t and two additional substituents in 3-and 6-position. Two of the eight naturally occurring stereoisomeric inositols (1,2,3,4,5,6-hexahydroxycyclohexanes) meet these demands, namely allo- (1,2,3,4/5,6) and neo- (1,2,3/4,5,6) inositol. If the mentioned two substituents in 3-and 6-position should not break the symmetry of the building block, only the neo-isomer comes into consideration. Whereas myo- (1,2,3,5/4,6) inositol, which differs from neo-inositol only by the configuration of one stereocentre, is cheaply available, the required neo-inositol cannot be purchased in larger amounts. Some methods for the preparation of neo-inositol or its derivatives were reported but none of them were feasible [4]. We therefore developed anew efficient method for the preparation of neo-The crystal structure of the title compound unequivocally proves the correct stereochemistry of the product. The asymmetric unit contains two halfs of two symmetry independent molecules. The other two halfs were generated by inversion centres in both molecules, giving the (1,2,3/4,5,6) arrangement in an ideal chair conformation. The puckering parameters are Q =0 .611(2) Å, q = 3.27(1)°, j =0°.The conformation is closely related to the structure of neo-inositol [6]. However, the compactness of the structure reported here is very small, characterized by alow density (1.049 g·cm -3 ), in contrast to that in neo-inositol with an unusually high density (1.69 g·cm -3 ). Beside above-mentioned disordered methyl groups at one position of one molecule, there are only marginal differences in the conformations of the two molecules. Hence only one molecule is presented in the figure. Since the compound is centrosymmetric, the atoms C1 to C6 of the carbon skeletons are designated as C1, C2 i ,C 3 i ,C 1 i ,C 2a nd C3 (symmetry code i: 2-x,2-y,2-z).

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Section: Discussionmentioning

confidence: 99%

Crystal structure of 1r,2c,3c,4t,5t,6t-1,2,3,4,5,6-hexakistrimethylsilanyloxy- cyclohexane, C24H60O6Si6

Wessig¹,

Möllnitz²,

Kelling³

et al. 2011

Zeitschrift Für Kristallographie - New Crystal Structures

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“…[66][67][68] Scheme 16 shows diastereomeric inositols, amino inositols, and their derivatives synthesized from 1,3-acetals of myoinositol. 27,28,40,51,65,69,70 Comparison of the overall yields and the number of steps involved in converting myo-inositol to some of its derivatives (shown in Schemes 15 and 16) via 1,3-acetals and other intermediates is given below for illustration. Yield of Ins(1,2,3)P 3 in the 1,3-acetal mediated synthesis was 23% 57 while the synthesis not mediated by 1,3-acetal was 12%.…”

Section: Preparation Of Myo-inositol-13-acetals By the Reductive Clementioning

confidence: 99%

myo-Inositol 1,3-acetals as early intermediates during the synthesis of cyclitol derivatives

Gurale

Sardessai

Shashidhar

2014

Carbohydrate Research

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“…Since the discovery of the relationship between intracellular concentrations of phosphoinositols and the release of calcium ions from intracellular sources, the chemistry and biology associated with naturally occurring inositol derivatives has expanded into a contemporary area of research with brisk activity. − Orthoesters of myo -inositol have been extensively used as early intermediates for the synthesis of phosphoinositols, cyclitols and their derivatives, − metal complexing agents, , and natural products containing the cyclitol moiety. , Considerable efforts have been invested in obtaining chiral myo -inositol derivatives from these rigid symmetric triols, since they can be obtained in gram quantities swiftly from commercially available myo -inositol. myo -Inositol has the meso -configuration and hence preparation of chiral myo -inositol derivatives necessarily involves the destruction of its symmetry.…”

Section: Introductionmentioning

confidence: 99%

Clues from Crystal Structures Pave the Way to Access Chiral myo-Inositol Derived Versatile Synthons: Resolution of Racemic 4-O-Allyl-myo-Inositol-1,3,5-Orthoesters via Corresponding Dicamphanates by Crystallization

Patil

Shashidhar

Tamboli³

et al. 2017

Crystal Growth & Design

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Racemic 4-O-allyl-myo-inositol-1,3,5-orthoesters were resolved as the corresponding diastereomeric dicamphanates by crystallization from alcoholic solvents. Crystals of the two diastereomers of myo-inositol orthoacetate and one diastereomer each of myo-inositol orthoformate and myo-inositol orthobenzoate were obtained in >99% purity, on gram scale. The configuration of all these diastereomers was established by conversion to known chiral myo-inositol derivatives as well as by single crystal structure analysis. It is interesting to note that the procedures for the separation of diastereomeric myo-inositol orthoesters could be evolved due to the knowledge of crystal growth and crystal structures of inositol derivatives of comparable molecular structures. Due to the synthetic versatility of myo-inositol orthoesters, the methods described provide rapid and convenient access to a variety of chiral inositol derivatives with high synthetic potential.

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A Short and Efficient Route from myo- to neo-Inositol

Cited by 12 publications

References 17 publications

Crystal structure of 1r,2c,3c,4t,5t,6t-1,2,3,4,5,6-hexakistrimethylsilanyloxy- cyclohexane, C24H60O6Si6

Crystal structure of 1r,2c,3c,4t,5t,6t-1,2,3,4,5,6-hexakistrimethylsilanyloxy- cyclohexane, C24H60O6Si6

myo-Inositol 1,3-acetals as early intermediates during the synthesis of cyclitol derivatives

Clues from Crystal Structures Pave the Way to Access Chiral myo-Inositol Derived Versatile Synthons: Resolution of Racemic 4-O-Allyl-myo-Inositol-1,3,5-Orthoesters via Corresponding Dicamphanates by Crystallization

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