The first hetero-bifunctionalization of the secondary face of β-cyclodextrin: selective and efficient conversion of the A-ring of a 2A,2B-disulfonate to 2A,3A-epoxymannoside

Fukudome, Makoto; Sugimoto, Yukihiko; Yuan, De‐Qi; Fujita, Kahee

doi:10.1039/b502573g

Cited by 7 publications

(2 citation statements)

References 12 publications

(9 reference statements)

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“…3 Moreover, no hetero-bifunctionalization of the secondary hydroxyl sides had been reported until we recently demonstrated the efficient synthesis of 2 from 2 A ,2 B -O,O-di(mesitylenesulfonyl)-b-CD 1 (Scheme 1). 4 Herein we report the selective synthesis of alloepithio-sulfonate 3 and an unexpected tandem reaction of 3 to generate the first tetracyclic residue within the macrocycle belt.…”

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Selective modification of β-cyclodextrin: an unexpected tandem reaction enables the cross-linking of C2A and C2B via a sulfur atom

et al. 2007

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Selective modification of β-cyclodextrin: an unexpected tandem reaction enables the cross-linking of C2A and C2B via a sulfur atom

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“…[9] In the case of the primary rim of CDs only two patterns of tridifferentiation are so far selectively accessible: a tridifferentiated b-CD based on the regioselective opening of a 6 A ,6 B -cap [10] and an asymmetric 6 A ,6…”

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Chemical Clockwise Tridifferentiation of α‐ and β‐Cyclodextrins: Bascule‐Bridge or Deoxy‐Sugars Strategies

Bistri

Sînaÿ

Barbero

et al. 2007

Chemistry A European J

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The selective and efficient functionalisation of large concave molecules is a chemical challenge opening the door to various applications, such as artificial enzymes. We propose here a method, based on deprotection of benzylated cyclodextrins, to selectively access a variety of complex structures with two or three new different functionalities on the primary platform. Our strategy is based on a mechanistic hypothesis involving the approach of an aluminium reagent between the primary oxygen atom and the endocyclic one of the same sugar unit. Due to its cyclic directionality, a change in steric hindrance on a given position of the cyclodextrin has a different effect on the clockwise or the counterclockwise directions. This concept is illustrated and exploited in two complementary ways: deoxygenation of the primary position of two diametrically opposed sugars induces a debenzylation reaction on the neighbouring clockwise sugars of alpha- and beta-cyclodextrins. Reversible capping, or bascule-bridging, of the same pair of sugars has the same effect on the debenzylation of alpha-cyclodextrin, but induces an important change of the geometry of beta-cyclodextrin, hence allowing the selective access to yet another functionalisation pattern. A combined use of deoxygenation and bascule-bridging allows the access to an alpha-cyclodextrin with its three pairs of primary functions differentiated and ready for further modifications. Bascule-bridge or deoxy-sugars are two complementary means to operate steric decompression and induce selective reactions to efficiently access a number of new patterns of functionalities on concave molecules.

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Three‐in‐One: Miniature Models of Natural Acyl‐Transfer Systems Enable Vector‐Selective Reaction on the Primary Side of Cyclodextrins

Yuan

Tominaga

fukuda

et al. 2022

Chemistry A European J

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The first hetero-bifunctionalization of the secondary face of β-cyclodextrin: selective and efficient conversion of the A-ring of a 2A,2B-disulfonate to 2A,3A-epoxymannoside

Abstract: The A-ring of 2(A),2(B)-O,O-di(mesitylenesulfonyl)-beta-cyclodextrin was converted to 2(A),3(A)-epoxymannoside without affecting the other sulfonylated residue, which affords the first approach to hetero-bifunctionalization at the secondary hydroxyl side of cyclodextrins.

Cited by 7 publications

References 12 publications

Selective modification of β-cyclodextrin: an unexpected tandem reaction enables the cross-linking of C2A and C2B via a sulfur atom

Selective modification of β-cyclodextrin: an unexpected tandem reaction enables the cross-linking of C2A and C2B via a sulfur atom

Chemical Clockwise Tridifferentiation of α‐ and β‐Cyclodextrins: Bascule‐Bridge or Deoxy‐Sugars Strategies

Three‐in‐One: Miniature Models of Natural Acyl‐Transfer Systems Enable Vector‐Selective Reaction on the Primary Side of Cyclodextrins

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