Directional control and supramolecular protection allowing the chemoand regioselective transformation of a triamine

Chemistry - A European Journal

Volumn 15, Issue 44, 2009, Pages 11912-11917

  Coquìre, David ^a   De La Lande, Aurélien ^b   Parisel, Olivier ^b   Prangé, Thierry ^c   Reinaud, Olivia ^a  

^a UNIVERSITÉ PARIS DESCARTES   (France)

^b LABORATOIRE DE CHIMIE THÉORIQUE   (France)

^c UNIVERSITÉ PARIS DESCARTES   (France)

Author keywords

Calixarenes; Host guest systems; Polyamines; Regioselectivity; Supramolecular chemistry

Indexed keywords

CALIX[6]ARENES; CALIXARENES; CARBAMOYLATION; COVALENT CHEMISTRY; DIRECTIONAL CONTROL; H-BONDING; HIGH SELECTIVITY; HOST-GUEST SYSTEM; IMIDAZOLYL; MULTIPLE INTERACTIONS; MULTIPOINT; POLYAMINES; REGIO-SELECTIVE; UNSYMMETRICAL;

AMINES; COORDINATION REACTIONS; MACROMOLECULES; PHENOLS; REGIOSELECTIVITY; STEEL BEAMS AND GIRDERS; ZINC;

SUPRAMOLECULAR CHEMISTRY;

CALIXARENE; NITROGEN; POLYAMINE; WATER; ZINC;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; CONFORMATION; ENZYME SPECIFICITY; STEREOISOMERISM; X RAY DIFFRACTION;

CALIXARENES; MODELS, MOLECULAR; MOLECULAR CONFORMATION; NITROGEN; POLYAMINES; STEREOISOMERISM; SUBSTRATE SPECIFICITY; WATER; X-RAY DIFFRACTION; ZINC;

EID: 72949119821     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200901020     Document Type: Article

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22. B' stands for the tricationic complex hosting the monoprotonated triamine with coordination of N1 to Zn. C' stands for the tetracationic complex hosting the diprotonated triamine with coordination of N8 to Zn. See the Supporting Information for their schematized and modeled structures. Crystals are triclinic, space group P1̄ with a=17.492(1), b= 23.610(2), c=25.639(1); a=102.69(1), b=105.96(1), g=90.60(1)8 and Z=4. The structure comprises 226 non-hydrogen atoms, that were refined against 13521 Fobs with R=8.65%. CCDC 713662 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/ cif. See also the Supporting Information.
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29. (i)According to the 1H NMR spectrum of the crude complex after reaction with Boc2O (and before precipitation with ether), the conversion is quasi-quantitative. This attests to the sequential endo-binding ii) reaction of the triamine, and not the reverse. Full characterization of the Boc-triamine, either included in the calixarene cavity or free is given in the Supporting Information. The stoichiometric reaction of ZnII, triamine and (Boc)2O with or without Et3N leads to an inextricable mixture of products, which means that coordination of ZnII to the triamine out of the calix cavity does not efficiently protect it from reacting with (Boc)2O, although it certainly slows down the carbamylation.