Chemoenzymatic Synthesis of Inositols, Conduritols, and Cyclitol Analogues

Abstract

Introduction 4223 2. Brief History of Inositol Chemistry 4224 3. Synthesis of Inositols and Conduritols from Cyclohexadiene-cis-1,2-diols 4227 3.1. Synthesis of Inositols 4227 3.2. Synthesis of Conduritols 4231 4. Synthesis of Functional and Structural Analogues of Inositols and Conduritols from Cyclohexadiene-cis-1,2-diols 4233 4.1. Synthesis of Conduramines 4233 4.2. Synthesis of Natural Products 4235 4.3. Synthesis of Other Analogues 4238 5. Synthesis via Enzymatic Resolution of Racemic Mixtures and Desymmetrization of Meso Compounds 4244 6. Synthesis via Enzyme-Catalyzed CarbonÀCarbon Bond Formation 4252 7. Conclusions and Future Prospects 4253 Author Information 4254 Biographies 4254 Acknowledgment 4255 References 4255

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

“…Inositols are a family of biologically relevant compounds [1–2] constituted by nine stereoisomeric hexahydroxycyclohexanes (Fig. 1): five have been found in nature ( myo , scyllo , D-chiro , L-chiro , and neo ), while the remaining four are unnatural synthetic products ( cis , epi , allo , and muco ).…”

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

“…Many of these intermediates have been synthesized from benzene, quinic acid, carbohydrates, and naturally occurring inositol derivatives. [17][18][19][20][21][22] myo-Inositol (1) is perhaps the most frequently used starting material for the synthesis of phosphoinositols and their analogs. This is because myo-inositol is relatively inexpensive and the relative reactivity of its hydroxyl groups as well as those of its derivatives is quite well understood.…”

“…Reaction of myo-inositol with trialkyl-orthoesters results in the formation of myo-inositol-1,3,5-orthoester as the sole product in high yield (Scheme 3), wherein three hydroxyl groups are protected simultaneously. [37][38][39][40][41][42] Due to the strong intramolecular hydrogen bonding between the C4-and C6-hydroxyl groups of myo-inositol orthoesters, and differences in the ability of the hydroxyl groups (of [18][19][20][21][22] to form chelates with metal ions, reaction of the hydroxyl groups of these orthoesters with alkyl halides can be controlled to obtain mono-, di-or, triethers exclusively (Scheme 3). [43][44][45] Hence a variety of orthogonally protected myo-inositol derivatives can be obtained in a short time.…”

Kinetic resolution of a precursor for myo-inositol phosphates under continuous flow conditions

“…On the other hand, enzyme-catalyzed kinetic resolutions are well known for their practicality, high efficiency and selectivity. Additionally, the separation of the formed derivative from the unreacted substrate is more easily accomplished, naturally [4][5][6][7].…”