AI Article Synopsis
- The regioselectivity of myo-inositol orthoesters’ sulfonylation can be manipulated using different bases, leading to selective sulfonate formations on specific hydroxyl groups.
- Monosulfonylation with sodium hydride or triethylamine targets the 4-hydroxyl group, while pyridine shifts the reaction to the 2-hydroxyl group; disulfonylation also varies based on the base used.
- These sulfonylated derivatives are stable during O-alkylation reactions but can be converted back to myo-inositol derivatives with specific reagents, proving valuable in synthesizing key myo-inositol phosphate compounds.
Article Abstract
The regioselectivity of sulfonylation of myo-inositol orthoesters was controlled by the use of different bases to obtain the desired sulfonate. Monosulfonylation of myo-inositol orthoesters in the presence of one equivalent of sodium hydride or triethylamine resulted in the sulfonylation of the 4-hydroxyl group. The use of pyridine as a base for the same reaction resulted in sulfonylation of the 2-hydroxyl group. Disulfonylation of these orthoesters in the presence of excess sodium hydride yielded the 4,6-di-O-sulfonylated orthoesters. However, the use of triethylamine or pyridine instead of sodium hydride yielded the 2,4-di-O-sulfonylated orthoester. Sulfonylated derivatives of myo-inositol orthoesters were stable to conditions of O-alkylation but were cleaved using magnesium/methanol or sodium methoxide in methanol to regenerate the corresponding myo-inositol orthoester derivative. These new methods of protection-deprotection have been used: (i) for the efficient synthesis of enantiomers of 2,4-di-O-benzyl-myo-inositol, which are precursors for the synthesis of D- and L-myo-inositol 1,3,4,5-tetrakisphosphate; (ii) for the preparation of 2-O-benzyl-myo-inositol which is a precursor for the preparation of myo-inositol 1,3,4,5,6-pentakisphosphate.
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| http://dx.doi.org/10.1016/s0008-6215(02)00298-7 | DOI Listing |
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