Programmed Synthesis of Hepta‐Differentiated β‐Cyclodextrin: 1 out of 117655 Arrangements

Abstract

Cyclodextrin poly‐functionalization has fueled progress in their use in multiple applications such as enzyme mimicry, but also in the polymer sciences, luminescence, as sensors or for biomedical applications. However, regioselective access to a given pattern of functions on β‐cyclodextrin is still very limited. We uncover a new orienting group, the thioacetate, that expands the toolbox available for cyclodextrin poly‐hetero‐functionalization using diisobutylaluminum hydride (DIBAL‐H) promoted debenzylation. The usefulness of this group is illustrated in the first synthesis of a precisely hepta‐hetero‐functionalized β‐cyclodextrin. By way of comparison, a random hepta‐functionalization would give 117655 different molecules. This synthesis is not simply the vain quest for the Holy Grail of CD hetero‐functionalization, but it illustrates the versatility of the DIBAL‐H oriented hetero‐functionalization strategy, opening the way to a multitude of useful functionalization patterns for new practical applications.

Multicharged cyclodextrin supramolecular assemblies

“…These groups not only give CDs excellent water solubility but also serve as convenient handles for derivatization. [41][42][43][44] However, since the C-6 hydroxy groups on the primary face are more reactive than the C-2 and C-3 hydroxyl groups on the secondary face, most reports are on the modification of the C-6 hydroxy groups to obtain mono-and per-substituted CDs, as well as site-selective poly-heterofunctionalized CDs, [45][46][47][48][49] although C-2 and C-3 hydroxy modifications are also used in the derivation of CDs. [50][51][52][53][54] Therefore, the regioselective modification of CDs is a very challenging issue that can further enrich the CD supramolecular assemblies and their applications in various fields.…”

Precise Rate Control of Pseudorotaxane Dethreading by pH-Responsive Selectively Functionalized Cyclodextrins

“…Here we wish to exploit the potential of selectively functionalized cyclodextrins (CDs) to modulate the kinetics of motion via the functionalization pattern on the CD by applying a stimulus directly on this macrocycle. Despite extensive use in polyrotaxane or slide-ring materials, CDs remain relatively underexploited as rings in rotaxane-based molecular machines .…”

Trendbericht Organische Chemie 2022

“…Wie Einsiedler und Gulder zeigen, hat die Dioxygenase AsqJ aus der Biosynthese des Naturstoffs Viridicatin neben ihrer natürlichen Funktion -der Umsetzung von Benzodiazepin-Substraten wie (136) zu Chinolonen (137) -eine bis dahin unentdeckte katalytische Aktivität. 92) Diese lässt sich durch einfache Variation der Seitenkette R in (136) ansteuern und erlaubt so, Chinazolinone (138) biokatalytisch herzustellen.…”

“…Ein besonderesCyclodextrin kommt von Sollogoubs Gruppe: Sie stellte das erste heptadifferenzierte β-Cyclodextrin her 136). Programmierte Synthese liefert selektiv eines aus 117655 denkbaren heptasubstituierten β-CD-Molekülen (Abbildung 44).Abb.…”