The 2-(Trimethylsilyl)ethyl Sulfur Group in Synthesis

Chambert, Stéphane; Désiré, Jérôme; Décout, Jean‐Luc

doi:10.1055/s-2002-35231

Cited by 3 publications

(1 citation statement)

References 93 publications

(135 reference statements)

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“…The last step in the oligonucleotide synthesis involved the deprotection of the amine group using ammonium hydroxide at 55 °C. The Fmoc protecting group of oligonucleotide ON1 was removed, however, the cyanoethyl group as a base-labile protecting group of the thiol was not removed quantitatively from the oligonucleotide ON2 [54–58]. …”

Section: Resultsmentioning

confidence: 99%

DNA functionalization by dynamic chemistry

Kanlidere¹,

Jochim²,

Cal³

et al. 2016

Beilstein J. Org. Chem.

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SummaryDynamic combinatorial chemistry (DCC) is an attractive method to efficiently generate libraries of molecules from simpler building blocks by reversible reactions under thermodynamic control. Here we focus on the chemical modification of DNA oligonucleotides with acyclic diol linkers and demonstrate their potential for the deoxyribonucleic acid functionalization and generation of libraries of reversibly interconverting building blocks. The syntheses of phosphoramidite building blocks derived from D-threoninol are presented in two variants with protected amino or thiol groups. The threoninol building blocks were successfully incorporated via automated solid-phase synthesis into 13mer oligonucleotides. The amino group containing phosphoramidite was used together with complementary single-strand DNA templates that influenced the Watson–Crick base-pairing equilibrium in the mixture with a set of aldehyde modified nucleobases. A significant fraction of all possible base-pair mismatches was obtained, whereas, the highest selectivity (over 80%) was found for the guanine aldehyde templated by the complementary cytosine containing DNA. The elevated occurrence of mismatches can be explained by increased backbone plasticity derived from the linear threoninol building block as a cyclic deoxyribose analogue.

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Section: Resultsmentioning

confidence: 99%

DNA functionalization by dynamic chemistry

Kanlidere¹,

Jochim²,

Cal³

et al. 2016

Beilstein J. Org. Chem.

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Palladium-Catalyzed Arylation of Aryl Sulfenate Anions with Aryl Bromides under Mild Conditions: Synthesis of Diaryl Sulfoxides

et al. 2016

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Palladium-Catalyzed Arylation of Alkyl Sulfenate Anions

et al. 2015

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A unique palladium-catalyzed arylation of alkyl sulfenate anions is introduced that affords aryl alkyl sulfoxides in high yields. Due to the base sensitivity of the starting sulfoxides, sulfenate anion intermediates, and alkyl aryl sulfoxide products, the use of a mild method to generate alkyl sulfenate anions was crucial to the success of this process. Thus, a fluoride triggered elimination strategy was employed with alkyl 2-(trimethylsilyl)ethyl sulfoxides to liberate the requisite alkyl sulfenate anion intermediates. In the presence of palladium catalysts with bulky monodentate phosphines (SPhos and Cy-CarPhos) and aryl bromides or chlorides, alkyl sulfenate anions were readily arylated. Moreover, the thermal fragmentation and the base promoted elimination of alkyl sulfoxides was overridden. The alkyl sulfenate anion arylation exhibited excellent chemoselectivity in the presence of functional groups, such as anilines and phenols, which are also known to undergo palladium catalyzed arylation reactions.

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The 2-(Trimethylsilyl)ethyl Sulfur Group in Synthesis

Cited by 3 publications

References 93 publications

DNA functionalization by dynamic chemistry

DNA functionalization by dynamic chemistry

Palladium-Catalyzed Arylation of Aryl Sulfenate Anions with Aryl Bromides under Mild Conditions: Synthesis of Diaryl Sulfoxides

Palladium-Catalyzed Arylation of Alkyl Sulfenate Anions

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