Model Compound 4. The monomer unit 2,2-bis(hydroxymethyl)propanoic acid was selected for the preparation of dendrimer 4. The fourth generation dendrons [G-4] that compose 4 were synthesized using a double stage convergent approach as reported previously (37). In summary, two analogues of the monomer were prepared: the protected acid and the protected 1,3-diol. The protecting groups selected were a benzyl ester group and an isopropylidene ketal group, respectively, to provide access to an orthogonal selective deprotection. The carboxylic acid functionality of the focal point can be deprotected by hydrogenolysis, while the diol surface becomes exposed upon acid-catalyzed hydrolysis of the ketal groups. The peripheral hydroxyl groups were esterified by reacting one equivalent of the protected acid diol (HO2-[G-1]-Bn) with two equivalents of the acid derivative of the monomer ([G-1]-COOH) in the presence of dicyclohexylcarbodiimide (DCC), forming the second generation dendron [G-2]. Following orthogonal deprotection of two samples of these [G-2] dendrons, the resulting [G-2]-OH4 and [G-2]-COOH dendrons were coupled under DCC conditions to afford the [G-4] dendron in one step.
For the assembly
Model Compound 4. The monomer unit 2,2-bis(hydroxymethyl)propanoic acid was selected for the preparation of dendrimer 4. The fourth generation dendrons [G-4] that compose 4 were synthesized using a double stage convergent approach as reported previously (37). In summary, two analogues of the monomer were prepared: the protected acid and the protected 1,3-diol. The protecting groups selected were a benzyl ester group and an isopropylidene ketal group, respectively, to provide access to an orthogonal selective deprotection. The carboxylic acid functionality of the focal point can be deprotected by hydrogenolysis, while the diol surface becomes exposed upon acid-catalyzed hydrolysis of the ketal groups. The peripheral hydroxyl groups were esterified by reacting one equivalent of the protected acid diol (HO2-[G-1]-Bn) with two equivalents of the acid derivative of the monomer ([G-1]-COOH) in the presence of dicyclohexylcarbodiimide (DCC), forming the second generation dendron [G-2]. Following orthogonal deprotection of two samples of these [G-2] dendrons, the resulting [G-2]-OH4 and [G-2]-COOH dendrons were coupled under DCC conditions to afford the [G-4] dendron in one step.For the assembly
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