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Graphical Abstract To create your abstract, type over the instructions in the template box below. Fonts or abstract dimensions should not be changed or altered. Tris-ACE-6,6’-bipyridyl--Cyclodextrin : Synthesis and Chirality of the Tripodal Metal Complexes Guillaume Poisson a , Florence Dumarçay-Charbonnier a and Alain Marsura a* Leave this area blank for abstract info. A novel heterotritopic -cyclodextrin tripod has been synthesized by the Staudinger-Aza-Wittig (SAW) reaction. Complexation properties and conformational events upon coordination with “hard” to“borderline” transition metals have been analyzed. Spontaneous formation of selective -helicity has been observed via the coordination with Cu II and Ni II cations.
Tetrahedron Letters journal homepage: www.elsevier.com Tris-ACE-6,6’-bipyridyl--Cyclodextrin : Synthesis and Chirality of the Tripodal Metal Complexes Guillaume Poisson a , Florence Dumarçay-Charbonnier a and Alain Marsura a* a SRSMC, Nancy Université & CNRS, Faculté des Sciences et Techniques, B. 70239, F-54506 Vandœuvre-lès-Nancy Cedex, France. Fax: +33 (0)3 83 68 23 45; Tel: +33 (0)3 83 68 49 55; E-mail: Alain.Marsura@pharma.uhp-nancy.fr ARTICLE INFO ABSTRACT Article history: Received Received in revised form Accepted Available online Keywords: tris- ACE --Cyclodextrin metallocyclodextrins Circular Dichroism helicates In the past decade, seminal work describe the preparation and properties of new metallocyclodextrins (metallo-CyDs) molecular receptors. 1 Metallo-CyDs architectures are potentially able to act in a wide range of applications such as: biomimetic catalysts, 2a-c photoactive devices, 3a-c chemical sensors 4a-b due to their properties after coordination to metals and formation of host-guest complexes with small invited molecules. A few years ago one of our research has concern the synthesis and complexation properties of a novel symmetrical ureido-5,5’bipyridyl--CyD tripode. 5 As expected, selective dual metal complexation and fluorescence properties controlled via HSAB metal classification were detected and analyzed. Nevertheless, considering the conformational aspects, the ureido-5,5’-bipyridyl tethers were found unable to generate expected chiral triple helices after coordination with appropriate metal cations. It is well known that spontaneous folding into a helical secondary structure is based on a general molecular self-organization process enforced by the conformational information encoded within the primary structure of the molecular strand itself. 6 Key features which determine the outcome of the assembly process are the ligand design, flexibility of the linker groups joining the coordination sites and the stereochemical preferences of the coordinating metal ion. 7 Failure in the helicate formation with ureido-5,5’-bipyridyl--CyD tripod was certainly due to an improper preorganization (orientation) and have motivated the synthesis of novel C 3-symmetrical tris-ACE-6,6’-bisheterocylic--CyDs in which the heterocyclic unit is anchored at the 6-position. Surprisingly, this minor modification, induces a dramatic change into the conformation of the ureido-bisheterocyclic strands around the upper-rim of the rigid CyD core. This letter describes the synthesis of a novel C3-symmetrical tris-ACE-6,6’-bis-heterocylic-- CyD via “one-pot” Staudinger-Aza-Wittig reaction (SAW). Metal complexation behavior was investigated by Uv-Vis and circular dichroism. Coordination of 6,6’-bipyridyl units with Cu II and Ni II cations, spontaneously generates a strong exciton coupling-type positive Cotton effect proving the formation of a -helix with a left-handed screw propeller (M). 2009 Elsevier Ltd. All rights reserved. iii N N reflux, 90min, h N N N N PPh 3/NH 4OH 10% OH 6 HO B, D, F Br A, C, E AcO B, D, F i ii OH OH 5 6 7 12 12 AcO B, D, F B, D, F 1 2 AcO 8 9 NBS/AIBN/CCl 4 N N 4 OAc 12 N N HN N H OAc 12 H 2N N3 A, C, E C O + A, C, E N N Scheme 1 : Synthetic pathway of 9 4 Br OAc 12 A, C, E 1 3 Br N3 H 2N NaN 3/DMSO SAW i = NBS/PPh 3/DMF ii = Ac 2O/pyridin; 7h, 80°C iii = NaN 3/DMF; 72h, 60°C SAW = PPh 3/DMF/CO 2 + 4
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AVERTISSEMENT Ce document est le fr
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"Rien n'entraîne de plus grands ma
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Sommaire TABLE DES ABREVIATIONS…
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Sommaire III. SYNTHESE DES α-CYCLO
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INTRODUCTION
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INTRODUCTION ET OBJECTIFS compositi
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I. LES CYCLODEXTRINES Chapitre I :
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HO O HO HO O OH OH O HO O HO O O OH
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Chapitre I : ÉTAT DE L’ART parti
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O Chapitre I : ÉTAT DE L’ART N N
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O H 2 O H 2 HN Co 3+ Chapitre I :
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Chapitre I : ÉTAT DE L’ART Afin
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O N OHO N N OH N O N OH N HN HN (CH
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Chapitre I : ÉTAT DE L’ART Le Cy
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NH N NH O S O NH Chapitre I : ÉTAT
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21 Chapitre I : ÉTAT DE L’ART Fi
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Chapitre I : ÉTAT DE L’ART lanth
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(H 3CO)14 N N N N Os N 3+ N Chapitr
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O O N N N Co Chapitre I : ÉTAT DE
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HO O HO HO O OH O HO O OH HO O OH O
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I. SUBSTITUTION RADICALAIRE I.1 INT
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Ar-CH 3 CHAPITRE II : SYNTHÈSE Hé
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Aire du pic % CHAPITRE II : SYNTHÈ
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CHAPITRE II : SYNTHÈSE porté par
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CHAPITRE II : SYNTHÈSE minutes pou
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CHAPITRE II : SYNTHÈSE bcde acde a
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CHAPITRE II : SYNTHÈSE A B C D E
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I.2.2.4 Optimisation. CHAPITRE II :
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temps(h) 2,6 2,4 2,2 2,0 1,8 1,6 44
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CHAPITRE II : SYNTHÈSE I.2.4.2 Chl
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CHAPITRE II : SYNTHÈSE seulement 5
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CHAPITRE II : SYNTHÈSE bipyridine
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CHAPITRE II : SYNTHÈSE Les résult
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CHAPITRE II : SYNTHÈSE Afin de vé
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abs abs 1,90E+00 1,40E+00 9,00E-01
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0,012 0,010 0,008 0,006 0,004 0,002
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CHAPITRE II : SYNTHÈSE ___________
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CHAPITRE II : SYNTHÈSE Figure II.1
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CHAPITRE II : SYNTHÈSE A titre de
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CHAPITRE II : SYNTHÈSE Nous propos
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HO CHAPITRE II : SYNTHÈSE Pour obt
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CHAPITRE II : SYNTHÈSE Par manque
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CHAPITRE II : SYNTHÈSE II.2 2-AMIN
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O N H O + CHAPITRE II : SYNTHÈSE S
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CHAPITRE II : SYNTHÈSE Afin d'obte
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N N N N N N CHAPITRE II : SYNTHÈSE
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N N N N N N CHAPITRE II : SYNTHÈSE
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CHAPITRE III MESURES PHYSICO-CHIMIQ
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CHAPTIRE III : MESURES PHYSICO-CHIM
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[76] CHAPTIRE III : MESURES PHYSICO
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N N CH 3 O N N N NH O O O O O OAc A
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[78] [2(78):2Ru III ] CHAPTIRE III
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Figure III.41 Titrage UV-Visible de
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N N logβ11 = 5,27 ± 0,16 Figure I
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Les figures suivantes représentent
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CH 3 N N N NH S Le titrage de 84 pa
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[C] mol/L 1,0E-05 8,0E-06 6,0E-06 4
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Le suivi cinétique de la décroiss
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espèces. Le traitement des spectre
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Figure III.65 Titrage UV-Visible de
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Pour le Hg I , nous observons un l
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Le cas du nickel est un peu plus fa
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Conclusion Nous avons montré que l
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C H 3 CHAPTIRE III : MESURES PHYSIC
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Page 165 and 166: CH 3 84 CHAPTIRE III : MESURES PHYS
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Page 190 and 191: CONCLUSION GENRALE Au cours de ce t
Page 192: PARTIE EXPERIMENTALE
Page 195 and 196: qui est chauffé à reflux pendant
Page 197 and 198: Aspect : poudre blanche Rendement :
Page 199 and 200: Masse moléculaire : 199,25 g/mol R
Page 201 and 202: Masse moléculaire : 237,3 g/mol RM
Page 203 and 204: is(bromométhyl)-2,2’-bipyridine
Page 205 and 206: AcO O N 3 O OAc O OAc O AcO O OAc A
Page 207 and 208: C H 3 S S mélange est laissé sous
Page 209 and 210: 6 A ,6 C ,6 E -tris-(6-méthylèneu
Page 211 and 212: Rendement : quantitatif Formule bru
Page 213 and 214: 6 A ,6 C ,6 E -tris-(6-méthylènet
Page 218 and 219: 2 The C3-symmetrical tris-ACE-6,6
Page 220: 4 Acknowledgments This work was sup
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