Assembly of [2]Rotaxanes in Water. Issue 28 (26th July 2017)

• Record Type: Journal Article
• Authors: Aeschi, Yves; Drayss‐Orth, Sylvie; Valášek, Michal; Raps, Felix; Häussinger, Daniel; Mayor, Marcel
• Is Part Of: European journal of organic chemistry. Issue 28(2017)
• Page Start: 4091
• Page End: 4103
• Publication Date: 2017-07-26
• Subjects: Rotaxanes -- Click chemistry -- Cyclophanes -- Host–guest systems; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201700640
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : Two [2]rotaxanes have been assembled in water from modular subunits through Cu I ‐catalyzed azide–alkyne "click" chemistry. For this purpose, 2, 6‐disubstituted naphthalene axles with solubilizing oligo(ethylene glycol) (OEG) chains ( n = 1–5) and propargyl terminal groups were synthesized and examined for their propensity to form inclusion complexes with a dicationic Diederich‐type cyclophane host. The dependence of pseudorotaxane formation on the linkers between the naphthalene core and OEG chains, and in the case of ester linkers on different spacer lengths, was analyzed by titration experiments. In addition, the inclusion complexes of two [2]rotaxanes were trapped by using a water‐soluble azide‐functionalized stopper. Repetitive chromatography finally enabled the isolation of both mechanically interlocked [2]rotaxanes. Abstract : Two [2]rotaxanes have been assembled in water from 2, 6‐disubstituted naphthalene axles with solubilizing oligo(ethylene glycol) and propargyl terminal groups, a dicationic Diederich‐type cyclophane, and an azide‐functionalized stopper by Cu I ‐catalyzed azide–alkyne "click" chemistry. The dependence of the initial pseudorotaxane formation on the axle structure was analyzed by titration experiments.