Regioselective difunctionalization of cyclodextrins

Petrillo, Marta; Marinescu, Lavinia; Bols, Mikael

doi:10.1007/s10847-010-9775-7

Cited by 6 publications

(5 citation statements)

References 29 publications

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“…[14,24] Other innovative methods to regioselectively functionalize CDs include selective diisobutylaluminium hydride (DIBAL-H)-promoted benzyld eprotection, [25][26][27] tandema zide reduction/deprotection, [28] tritylations, [29] and introduction of biselectrophiles. [30] Monoderivatizationo ft he b-CD primary rim with ad esiredf unctionalg roup often necessitates multiple synthetic steps. Usually,t his is achieved by the monotosylation of ap rimary alcohol followed by nucleophilic displacement.…”

Section: Introductionmentioning

confidence: 99%

Access to Versatile β‐Cyclodextrin Scaffolds through Guest‐Mediated Monoacylation

Vurgun

Gómez‐Biagi

Nitz

2015

Chemistry A European J

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Herein, we report the selective mono-derivatization of heptakis[6-deoxy-6-(2-aminoethylsulfanyl)]-β-CD (1) through a guest-mediated covalent capture strategy. The use of guests functionalized with cleavable linkers enables the installation of an amine-orthogonal thiol group on the primary rim of 1 as a handle for further transformations to the β-CD scaffold. Applying this methodology, two novel monoderivatized β-CDs were obtained in good yield and high purity. Both of these monoacylated CDs were amenable to facile linker cleavage and further modification at the resulting thiol group. This methodology can be applied towards the synthesis heterofunctionalized β-CD constructs for analyte sensing, drug delivery, and other applications.

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Section: Introductionmentioning

confidence: 99%

Access to Versatile β‐Cyclodextrin Scaffolds through Guest‐Mediated Monoacylation

Vurgun

Gómez‐Biagi

Nitz

2015

Chemistry A European J

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“…In natural glycans, such as HMOs, the fucosides are often separated by non‐fucosylated carbohydrate residues, making this 3A,3D pattern a highly relevant mimic. While the regioselective 6A,6D substitution of CDs is well‐developed for decoration of the primary rim, only limited examples of di‐substitutions on the secondary rim exist, and none of these examples covers a direct glycosylation reaction. We propose that the regioselectivity observed here arises from the kinetic conditions employed in the glycosylation reaction, that is, low temperatures and short reaction times.…”

Section: Discussionmentioning

confidence: 99%

Direct and Regioselective Di‐α‐fucosylation on the Secondary Rim of β‐Cyclodextrin

Verkhnyatskaya

Vries

et al. 2019

Chemistry A European J

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A straightforward glycosylation method is described to regio‐ and stereoselectively introduce two α‐ l ‐fucose moieties directly to the secondary rim of β‐cyclodextrin. Using NMR and MS fragmentation studies, the nonasaccharide structure was determined, which was also visualized using molecular dynamics simulations. The reported glycosylation method proved to be robust on gram‐scale, and may be generally applied to directly glycosylate β‐cyclodextrins to make well‐defined multivalent glycoclusters.

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“…In contrast, heterobifunctionalized CDs have been prepared via multistep synthesis (depending on the steric hindrance of the moiety on the CD scaffold and on the bulkiness of reagents [ 22 ]) or by modification of homobifunctionalized CDs [ 23 – 24 ]. These and previous studies [ 25 – 26 ] confirmed that CD derivatives with bulky substituents such as tosyl groups can be separated by reversed-phase column chromatography and HPLC separation methods can be easily scaled up to obtain grams of pure regioisomers.…”

Section: Introductionmentioning

confidence: 99%

Enhanced single-isomer separation and pseudoenantiomer resolution of new primary rim heterobifunctionalized α-cyclodextrin derivatives

Tichá

Benkovics

Jindřich

2018

Beilstein J. Org. Chem.

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The synthesis of batch-to-batch reproducible cyclodextrin (CD) derivatives often requires functionalization at specific positions of the CD skeleton. However, the regioselective preparation of this type of CD derivatives remains a challenge in synthetic chemistry. Thus, the present study aimed to prepare all positional regioisomers on the primary rim of homobifunctionalized diazido-α-CDs by selective substitution on the primary rim. Specifically, three positional regioisomers 6A,6B-, 6A,6C-, and 6A,6D-diazido-α-CDs were prepared via different intermediates (using sulfonylation with capping agents, bromination and tosylation). Furthermore, heterobifunctionalized 6A-azido-6X-mesitylenesulfonyl-α-CDs were also synthesized, and all regioisomers were successfully separated by HPLC. Moreover, the heterobifunctionalized α-CD regioisomers were isolated in gram-scale quantities, isomers AB and AC in the form of a pseudoenantiomeric mixture. The pseudoenantiomers AC/CA and AB/BA were resolved on an analytical scale by HPLC–MS at 10 °C. Thus, the presented synthetic and analytical methods for homo- and heterodisubstituted α-CDs are efficient and reproducible for the preparation of various pure regioisomeric CD derivatives. Accordingly, our findings indicate, (i) the versatility of selectively modified azido and mesitylene CD skeletons in preparing new types of α-CD derivatives and (ii) the potential of using resolved α-CD pseudoenantiomers in other research fields such as organocatalysis.

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Regioselective difunctionalization of cyclodextrins

Cited by 6 publications

References 29 publications

Access to Versatile β‐Cyclodextrin Scaffolds through Guest‐Mediated Monoacylation

Access to Versatile β‐Cyclodextrin Scaffolds through Guest‐Mediated Monoacylation

Direct and Regioselective Di‐α‐fucosylation on the Secondary Rim of β‐Cyclodextrin

Enhanced single-isomer separation and pseudoenantiomer resolution of new primary rim heterobifunctionalized α-cyclodextrin derivatives

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