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Issue 27, 2017
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[PhSiO1.5]8,10,12 as nanoreactors for non-enzymatic introduction of ortho, meta or para-hydroxyl groups to aromatic molecules

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Abstract

Traditional electrophilic bromination follows long established “rules”: electron-withdrawing substituents cause bromination selective for meta positions, whereas electron-donating substituents favor ortho and para bromination. In contrast, in the [PhSiO1.5]8,10,12 silsesquioxanes, the cages act as bulky, electron withdrawing groups equivalent to CF3; yet bromination under mild conditions, without a catalyst, greatly favors ortho substitution. Surprisingly, ICl iodination without a catalyst favors (>90%) para substitution [p-IC6H4SiO1.5]8,10,12. Finally, nitration and Friedel–Crafts acylation and sulfonylation are highly meta selective, >80%. In principle, the two halogenation formats coupled with the traditional electrophilic reactions provide selective functionalization at each position on the aromatic ring. Furthermore, halogenation serves as a starting point for the synthesis of two structural isomers of practical utility, i.e. in drug prospecting. The o-bromo and p-iodo compounds are easily modified by catalytic cross-coupling to append diverse functional groups. Thereafter, F/H2O2 treatment cleaves the Si–C bonds replacing Si with OH. This represents a rare opportunity to introduce hydroxyl groups to aromatic rings, a process not easily accomplished using traditional organic synthesis methods. The as-produced phenol provides additional opportunities for modification. Each cage can be considered a nanoreactor generating 8–12 product molecules. Examples given include syntheses of 4,2′-R,OH-stilbenes and 4,4′-R,OH-stilbenes (R = Me, CN). Unoptimized cleavage of the Br/I derivatives yields 55–85% phenol. Unoptimized cleavage of the stilbene derivatives yields 35–40% (3–5 equivalents of phenol) in the preliminary studies presented here. In contrast, meta R-phenol yields are 80% (7–10 mol per cage).

Graphical abstract: [PhSiO1.5]8,10,12 as nanoreactors for non-enzymatic introduction of ortho, meta or para-hydroxyl groups to aromatic molecules

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Publication details

The article was received on 31 Jan 2017, accepted on 02 Mar 2017 and first published on 02 Mar 2017


Article type: Paper
DOI: 10.1039/C7DT00373K
Citation: Dalton Trans., 2017,46, 8797-8808
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    [PhSiO1.5]8,10,12 as nanoreactors for non-enzymatic introduction of ortho, meta or para-hydroxyl groups to aromatic molecules

    M. Bahrami, X. Zhang, M. Ehsani, Y. Jahani and R. M. Laine, Dalton Trans., 2017, 46, 8797
    DOI: 10.1039/C7DT00373K

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