Vinyl sulfonyl chemistry-driven unidirectional transport of a macrocycle through a [2]rotaxane

• Published in: Organic chemistry frontiers an international journal of organic chemistry 2022-02, Vol.9 (3), p.633-642
• Main Authors: David, Arthur H G, Pablo García–Cerezo, Campaña, Araceli G, Francisco Santoyo–González, Blanco, Victor
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Decoupling; Michael reaction; NMR; Nuclear magnetic resonance; Organic chemistry; Rotaxanes; Sulfonates; Vinyl sulfone
• ISSN: 2052-4110; 2052-4110
• DOI: 10.1039/d1qo01491a

By applying a combination of the coupling-and-decoupling (CAD) chemistry of the vinyl sulfonate group with the click thia-Michael addition to the vinyl sulfone group (MAVS) we performed the irreversible unidirectional transportation of the ring through the linear component in a [2]rotaxane by a chemically and pH-driven flashing energy ratchet mechanism. The design is based on a monostoppered thread precursor bearing a sulfonate stopper, a vinyl sulfone group on the unstoppered end and a dibenzylammonium unit as recognition site for the dibenzo-24-crown-8 macrocycle. First, the ring enters from the vinyl sulfone side and the rotaxane is capped through a thia-Michael addition reaction. Then, the cleavage of the sulfonate group of the opposite stopper using MgBr2 as chemical stimulus and subsequent addition of base (Et3N) promoted the controlled and directional release of the macrocycle into the bulk under mild conditions. The efficiency of the system allowed the in situ operation as demonstrated by NMR and HRMS techniques.