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A Hexavalent Basket for Bottom‐Up Construction of Functional Soft Materials and Polyvalent Drugs through a “Click” Reaction
Author(s) -
Neal Taylor A.,
Wang Weikun,
Zhiquan Lei,
Peng Ruojing,
Soni Priti,
Xie Han,
Badjić Jovica D.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805246
Subject(s) - azide , combinatorial chemistry , chemistry , cycloaddition , functional group , click chemistry , chemoselectivity , supramolecular chemistry , reactivity (psychology) , molecule , anthracene , hydrolysis , organic chemistry , catalysis , polymer , medicine , alternative medicine , pathology
Inspired by polyvalency and its prevalence in nature, we developed an efficient synthetic route for accessing a large variety of multivalent and dual‐cavity baskets from inexpensive and abundant starting materials. First, the cycloaddition of vinyl acetate to anthracene was optimized to, upon hydrolysis, give dibenzobarrelene derivative 6 , which after five functional group transformations and then cyclotrimerization gave heptiptycene dodecaester 4 in an overall 17 % yield. Following that, compound 4 was converted into D 3 h symmetric 1 , composed of two fused cavitands each holding three terminal alkynes at the rim for conjugation to functional molecules using the highly efficient CuAAC reaction. To survey the reactivity of hexavalent 1 , we “clicked” 2‐acetamido‐2‐deoxy‐β‐ d ‐glucopyranosyl azide 3,4,6‐triacetate (carbohydrate), methoxypolyethylene glycol azide (PEG, M n =2000; polymer) and benzyl azide (aromatic) to obtain hexavalent conjugates 12 – 14 in 50–79 % yields. In summary, dual‐cavity 1 is an accessible, structurally‐unique and hexavalent host that can be “clicked” to a variety of functional molecules for (a) combinatorial lead identification of drugs, (b) preparation of hierarchical soft materials and (c) design of selective chemosensors, scavengers, or supramolecular catalysts.