Organoiron Route to a New Dendron for Fast Dendritic Syntheses Using Divergent and Convergent Methods

Sartor, Valérie; Djakovitch, Laurent; Fillaut, Jean‐Luc; Moulines, Françoise; Neveu, Frédéric; Marvaud, Valérie; Guittard, Frédéric; Blais, Jean‐Claude; Astruc, Didier

doi:10.1021/ja983868m

Cited by 114 publications

(90 citation statements)

References 32 publications

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“…The hexahapto complexation of arenes by the cationic group CpFe + considerably increases the acidity of its benzylic protons (the pKa's of the arenes in DMSO are lowered upon complexation with CpFe + by approximately 15 units, for instance from 43 to 28 for C 6 Me 6 ) [24][25][26]. Therefore, deprotonation of the CpFe(arene) + complexes is feasible under mild conditions with KOH.…”

Section: Combining Cpfe + -Induced Arene Perfunctionalization With Olmentioning

confidence: 99%

“…[26][27][28][29]. Pentamethylcobalticinium was perallylated to yield a deca-allylated cobalticinium, and then RCM of the organometallic complex proceeded to afford a pentacyclopentelylcyclopentadienyl Co sandwich 3 complex using the catalyst [Ru(PCy 3 ) 2 Cl 2 (=CHPh)] [12].…”

Section: Equationmentioning

confidence: 99%

“…The activation of mesitylene upon complexation by the CpFe + moiety in [CpFe(mesitylene) + ][PF 6 -], followed by a one-pot perallylation yielded [CpFe(nonaallylmesitylene) + ] [PF 6 -], 9 (Scheme 9) [25,26]. First, triple RCM reaction catalyzed by [RuCl 2 (PCy 3 ) 2 (=CHPh)] proceeds in ten minutes under ambient condition, and a tetracyclic intermediate iron arene complex was isolated.…”

Section: Equationmentioning

confidence: 99%

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The Olefin Metathesis Reactions in Dendrimers

Astruc

2010

Green Metathesis Chemistry

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Résumé -Les réactions de métathèse des oléfines dans les dendrimères -Les réactions de métathèse avec les dendrimères récemment étudiées dans notre groupe de recherche sont brièvement résumées dans cette micro revue. Celles-ci incluent les réactions qui impliquent des catalyseurs de métathèse métallodendritique comportant des terminaisons bis-phosphines coordonnées au catalyseur de métathèse centré sur le ruthénium (polymérisation) et les réactions de peralkylation des polyméthylarènes induites par complexation temporaire de ces arènes avec le greffon CpFe + (Cp = η 5 -C 5 H 5 ) couplée avec la métathèse (RCM et croisée), catalysée par les catalyseurs de Grubbs de première et seconde généra-tion. Un exemple de la remarquable chemio-, régio-et stéréosélectivité de la métathèse croisée avec l'acide acrylique est mentionné, permettant d'accéder à des dendrimères hydrosolubles par fonctionnalisation des branches oléfiniques terminales. La revue mentionne également la polymérisation des alcynes terminaux par métathèse polymérisante dont la vitesse est considérablement accrue par couplage avec un catalyseur de transfert d'électron en chaîne. Abstract -The Olefin Metathesis Reactions in Dendrimers -Olefin metathesis reactions catalyzed by Ru benzylidene catalysts involving polymers and dendrimers have been investigated in our research group and are briefly reviewed. Dendrimers have been loaded at their periphery with rutheniumchelating bis-phosphines, which leads to the formation of dendrimer-cored stars by ring-openingmetathesis polymerization (ROMP

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Section: Combining Cpfe + -Induced Arene Perfunctionalization With Olmentioning

confidence: 99%

Section: Equationmentioning

confidence: 99%

Section: Equationmentioning

confidence: 99%

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The Olefin Metathesis Reactions in Dendrimers

Astruc

2010

Green Metathesis Chemistry

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“…Among these, the temporary complexation of aromatics by 12-electron organotransition metal units provides a powerful means to activate aromatics towards nucleophilic and deprotonation reactions. [11] In this context, Astruc et al, have developed an original way to prepare dendrimers and dendrons, using a synergy between two modes of aromatic activation by the electron-withdrawing cation CpFe + : the enhanced acidity of the benzylic protons and the nucleophilic cleavage of the O-alkyl bond of phenyl ether complexes. Thus, they have shown that the perfunctionalization and heterolytic cleavage of the O-alkyl bond of phenyl ether complex 1c in a one-pot reaction, nine sequence, directly lead to a dendron.…”

Section: Introductionmentioning

confidence: 99%

Fast and Scalable Route to Aryl Polyallyl Dendrons and Dendrimers

et al. 2008

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In the quest for general and efficient synthetic procedures for dendrons and dendrimers, allylphenol, allylnaphthol and 6-bromonaphthalene AB 3 dendrons have been successfully prepared on a large-scale by a rapid and clean route starting from commercially available esters and allyl bromide. In contrast to the known organoiron strategy, the above-mentioned methodology enables the largescale synthesis of AB 3 dendrons in only two days.

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“…This latter reaction is the most commonly used one in our laboratory, as it is so easy and convenient to carry out on a large scale either using potassium tert-butoxide or potassium hydroxide. The nona-allyl aromatic obtained can be hydroborated 9 or hydrosilylated 9,11 for further dendrimer construction using a phenoltriallyl brick (dendron A in Scheme 1) 12 that allows multiplying the number of branches by three at each dendritic generation. The largest dendrimers known have been built in this way and characterized until the 9 th generation bearing a theoretical number of 3 11 branches, 11 for the first time far beyond the de Gennes "dense-packing" limit 13 (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%