Publication
Article Metrics
Citations
Online attention
Spontaneous assembly of rotaxanes from a primary amine, crown ether and electrophile
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)