Selectivity in cyclic acetal hydrolyses: a comparison between cis- and trans- fused benzylidene rings

Lehmann, Jochen; Schwesinger, Berit

doi:10.1016/s0008-6215(00)83947-6

Cited by 4 publications

(3 citation statements)

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“…Hydrolysis of benzylidene acetal groups of monosaccharides. (a) Faster hydrolysis of benzylidene acetal groups of Glc and Man rather than that of Gal as previously reported. , (b) Selective hydrolysis of trans -fused benzylidene acetal group in the presence of cis -fused benzylidene acetal group as previously reported . (c) Representative reaction scheme performed in this study.…”

Section: Introductionmentioning

confidence: 55%

“…7,8 (b) Selective hydrolysis of trans-fused benzylidene acetal group in the presence of cis-fused benzylidene acetal group as previously reported. 9 (c) Representative reaction scheme performed in this study. [ln(k/T) versus 1/T] gave a linear line as shown in Figure 2c,d.…”

Section: ■ Resultsmentioning

confidence: 99%

“…In addition, Lehmann et al demonstrated selective cleavage of a trans-fused benzylidene acetal group in the presence of a cisfused one (Figure 1b). 9 As mentioned previously, there are some examples showing selective deprotection of the benzylidene acetal group, and therefore, these results need to be rationally interpreted because acceleration and deceleration factors of hydrolysis of benzylidene acetal groups are not understood well.…”

Section: ■ Introductionmentioning

confidence: 99%

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Acceleration and Deceleration Factors on the Hydrolysis Reaction of 4,6-O-Benzylidene Acetal Group

et al. 2020

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The benzylidene acetal group is one of the most important protecting groups not only in carbohydrate chemistry but also in general organic chemistry. In the case of 4,6-O-benzylidene glycosides, we previously found that the stereochemistry at 4-position altered the reaction rate constant for hydrolysis of benzylidene acetal group. However, a detail of the acceleration or deceleration factor was still unclear. In this work, the hydrolysis reaction of benzylidene acetal group was analyzed using the Arrhenius and Eyring plot to obtain individual parameters for glucosides (Glc), mannosides (Man), and galactosides (Gal). The Arrhenius and Eyring plot indicated that the pre-exponential factor (A) and ΔS ⧧ were critical for the smallest reaction rate constant of Gal among nonacetylated substrates. On the other hand, both E a /ΔH ⧧ and A/ΔS ⧧ were influential for the smallest reaction rate constant of Gal among diacetylated substrates. All parameters obtained suggested that the rate constant for hydrolysis reaction was regulated by protonation and hydration steps along with solvation. The obtained parameters support wide use of benzylidene acetal group as orthogonal protection of cis-and trans-fused bicyclic systems through the fast hydrolysis of the trans-fused benzylidene acetal group.

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