Solid‐phase synthesis of uniform linear oligoethers with repeating functional arms as multivalent spacers

Spasser, Liat; Portnoy, Moshe

doi:10.1002/pola.24382

Cited by 6 publications

(5 citation statements)

References 37 publications

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“…[35][36][37][38][39][40][41] Whereas the assembly of the hydrophobic branchesi sa chieved via the reductiono ft he ester groups of this scaffold, three different synthetic routes were examined for the introduction of the imidazole moiety near the focal point of the future dendron (the phenol hydroxy function). [35][36][37][38][39][40][41] Whereas the assembly of the hydrophobic branchesi sa chieved via the reductiono ft he ester groups of this scaffold, three different synthetic routes were examined for the introduction of the imidazole moiety near the focal point of the future dendron (the phenol hydroxy function).…”

Section: Resultsmentioning

confidence: 99%

“…We decided to base the synthesis on the 5‐hydroxyisophthalate scaffold, used by us multiple times on previous occasions for the design of dendritic molecules . Whereas the assembly of the hydrophobic branches is achieved via the reduction of the ester groups of this scaffold, three different synthetic routes were examined for the introduction of the imidazole moiety near the focal point of the future dendron (the phenol hydroxy function).…”

Section: Resultsmentioning

confidence: 99%

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Chemoselectivity Improvement via Partial Shielding of an Imidazole Active Site in Branched/Dendritic Homogeneous Catalysts of the Baylis–Hillman Reaction

2016

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While comparing analogousp olystyrenesupported and homogeneous catalysts for the Baylis-Hillmanr eaction, we hypothesized that the hydrophobice nvelopment of the imidazole catalytic sites of the former is responsible for the significantly better chemoselectivity exhibited by the heterogeneous catalysts compared to theirh omogeneousc ounterparts.I no rder to test this hypothesis,w ep repared as eries of branched/dendritic homogeneousc atalysts,w ith an imidazole active site near the focal point andf lexiblet ails of various lengthsa nd polarities,c apable of providing partials hieldingo ft his site.T he design of the catalysts was based on a5 -hydroxyisophthalate scaffold,a nd they were prepared throughanumber of multistep synthetic pathways. Thec omparison of the catalysts under av arietyo f conditions in am odel Baylis-Hillman reactiond emonstrated that long hydrophobic tales enhance the chemoselectivity parameter of the catalysis,w hile reducing the rate of the consumptiono ft he substrates, and that the chemoselectivity is further improvedb y the presence of af ree phenolic moiety in the vicinity of the catalytic imidazole unit. Moreover, in secondgeneration catalysts,t he peripherall ong tails could be either hydrophobic or polar, since the dendritic inner backbone itself presumably partially provides the necessary isolation of the catalytic site.T hus,e xperimental results support our hypothesis.Synthesis of 1,3-bis(methoxymethyl)-5-(methoxymethoxy)benzene: Thec ompound was prepared according to the typical procedure for the benzylic alcohol alkylation, using the followingq uantities:i odomethane (1.68 mL, 28.0 mmol, 4.0 equiv.), [5-(methoxymethoxy)-1,3-phenylene]dimethanol

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Chemoselectivity Improvement via Partial Shielding of an Imidazole Active Site in Branched/Dendritic Homogeneous Catalysts of the Baylis–Hillman Reaction

2016

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“…Synthesis of the G3 DE Dendron (19). The G3 DE dendron (19) was synthesized on a 0.05 mmol scale as described for 16.…”

Section: Optimization Of Solid Phase Dendron Synthesis (Spds) Model P...mentioning

confidence: 99%

Access to Diverse Glutamic Acid Dendrons and a Janus Peptide Dendrimer Using an Atypical Solid Phase Synthesis

Singh,

Mandal,

Chakravarty

2024

J. Org. Chem.

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The negligible cytotoxicity of anion surface-linked dendrons makes glutamic acid-based dendrons a potential candidate for materials and biological applications. Despite the inherent drawbacks of the conventional solution phase synthesis of glutamic acid-based dendrons, there have been no advancements in these protocols. Herein, we demonstrate the first-ever convergent solid phase synthesis of dendrons, up to fourth generation, having glutamic acid branching points produced by preactivation of dicarboxylic acid groups with N-hydroxysuccinimide and simultaneous coupling with amine groups of two growing peptide chains, with excellent yields (30−70%). In addition to the general advantages, such as the easy workup, a final single purification step, and an overall short synthesis duration, the convergent solid phase synthesis allowed us to chemically synthesize glutamic acid branching-based dendrons that cannot be accessed by standard divergent solid phase synthesis. This method has also been validated for its application in synthesizing hard-to-achieve Janus peptide dendrimers in a single stretch on a solid support. Our work corroborates the efficacy of controlled -COOH activation to accomplish an atypical solid phase synthesis of diverse glutamic acid dendrons in a convergent fashion. This is the first example of a Janus peptide dendrimer being synthesized on a solid support, utilizing both convergent and divergent approaches simultaneously.

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“…It has greatly simplified the synthesis of complex biological macromolecules, such as peptides [23,24], oligonucleotides [25], and oligosaccharides [26e28], otherwise difficult to accomplish in solution. Solid-phase synthesis has also been implemented in the fabrication of structurally diverse small molecules [29] and polymers [30], as well as in combinatorial chemistry to construct new chemical entities and natural productlike libraries [31].…”

Section: Solid-phase Synthesismentioning

confidence: 99%

Solid-phase dendrimer synthesis: a promising approach to transform dendrimer construction

Huang

Kao

Selvaraj

et al. 2023

Materials Today Chemistry

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Solid‐phase synthesis of uniform linear oligoethers with repeating functional arms as multivalent spacers

Cited by 6 publications

References 37 publications

Chemoselectivity Improvement via Partial Shielding of an Imidazole Active Site in Branched/Dendritic Homogeneous Catalysts of the Baylis–Hillman Reaction

Chemoselectivity Improvement via Partial Shielding of an Imidazole Active Site in Branched/Dendritic Homogeneous Catalysts of the Baylis–Hillman Reaction

Access to Diverse Glutamic Acid Dendrons and a Janus Peptide Dendrimer Using an Atypical Solid Phase Synthesis

Solid-phase dendrimer synthesis: a promising approach to transform dendrimer construction

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