Elucidation of the acid reactivity of polyhedral orthoformates for the synthesis of carbasugar derivatives

TL;DR

The paper explains how the acid reactivity of certain chemical structures can be used to synthesize carbasugar derivatives more selectively.

Contribution

The study provides new insights into the acid reactivity of polyhedral orthoformates based on their isomerism and substituents using DFT calculations.

Findings

Methoxy olefin derivatives of orthoester-protected myo-inositols show different reaction selectivities based on geometric isomerism.

DFT calculations elucidated the mechanism behind the observed selectivity in acid reactivity.

The findings contribute to more efficient synthesis of carbasugar-type derivatives.

Abstract

Carbasugar-containing natural products such as uvaridacol L have a variety of bioactivities, motivating chemists to develop methods for their synthesis. The conversion of myo-inositol is one of the most efficient methods for the synthesis of carbasugars. However, selective conversion of myo-inositol derivatives remains to be explored. In our synthesis of uvaridacol L derivatives, we found that the methoxy olefin derivatives of orthoester-protected myo-inositols, the key synthetic intermediates of our study, exhibit differing reaction selectivities depending on their geometric isomerism and substituents. Here we present new insights that contribute to the synthesis of carbasugar-type derivatives by elucidating the mechanism of the selectivity using density functional theory (DFT) calculations.

We present new insights that contribute to the synthesis of carbasugar derivatives by elucidating the acid reactivity of polyhedral orthoformates depending on their geometric isomerism and substituents using DFT calculations.

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