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Spontaneous assembly of rotaxanes from a primary amine, crown ether and electrophile

DOI: 10.1021/jacs.8b03394 DOI Help

Authors: Stephen D. P. Fielden (University of Manchester) , David A. Leigh (University of Manchester) , Charlie T. Mcternan (University of Manchester) , Borja Pérez-Saavedra (University of Manchester) , Iñigo J. Vitorica-Yrezabal (University of Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: May 2018
Diamond Proposal Number(s): 17379

Abstract: We report the synthesis of crown ether-ammonium, amide and amine [2]rotaxanes via transition state stabilization of axle-forming reactions. In contrast to the two-step “clipping” and “capping” strategies generally used for rotaxane synthesis, here the components assemble into the interlocked molecule in a single, reagent-less, step under kinetic control. The crown ether accelerates the reaction of the axle-forming components through the cavity to give the threaded product in a form of metal-free active template synthesis. Rotaxane formation can proceed through the stabilization of different transition states featuring 5-coordinate (e.g., SN2) or 4-coordinate (e.g., acylation, Michael addition) carbon. Examples prepared using the approach include crown-ether-peptide rotaxanes and switchable molecular shuttles.

Journal Keywords: Macrocyclic compounds; Ethers; Rotaxanes; Transition states; Amines

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 08/05/2018 09:29

Discipline Tags:

Chemistry Organic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)