A Versatile Axle for the Construction of Disassemblage Rotaxanes

Abstract

Rotaxanes are unique mechanical devices that hold great promise as sensors. We report on two new rotaxanes that contain an acid or base sensitive trigger and readily disassemble in a wide range of environments. Disassemblage was observed under TLC and 1 H-NMR analysis. The axle is highly charged, which enhances solubility in aqueous environments, and can be readily derivatized with sensor components. The trigger was swapped in a one-pot method, which is promising for the rapid production of a series of sensors.

[2]Rotaxane End‐Capping Synthesis by Click Michael‐Type Addition to the Vinyl Sulfonyl Group

“…[25b, 29] However, the use of vinyl sulfonate derivatives gives the added value of allowing al ater cleavage through nucleophilic substitution of the sulfonate moieties obtained after the Michael-type addition, as we recently demonstrated. [28] This behaviour, which enables vinyl sulfonates as promisingr eagents for the so-called coupling-and-decoupling (CAD) chemistry, [30] could be interesting in the development of cleavable [31] functional rotaxanes, especially relevant for applications such as controlled delivery or directional transport, [32] if the decoupling step that leads to the disassembly of the components takes place under mild conditions. Therefore, here we report the development of an ew,e fficient and versatile methodology for the synthesis of rotaxanes based on the click Michael-type addition reaction [33] of thiols [34] or amines to vinyl sulfone and vinyl sulfonate moieties as the key reaction for the capping step.…”