Dataset Information

Protein modification via alkyne hydrosilylation using a substoichiometric amount of ruthenium(ii) catalyst.

ABSTRACT: Transition metal catalysis has emerged as a powerful strategy to expand synthetic flexibility of protein modification. Herein, we report a cationic Ru(ii) system that enables the first example of alkyne hydrosilylation between dimethylarylsilanes and O-propargyl-functionalized proteins using a substoichiometric amount or low-loading of Ru(ii) catalyst to achieve the first C-Si bond formation on full-length substrates. The reaction proceeds under physiological conditions at a rate comparable to other widely used bioorthogonal reactions. Moreover, the resultant gem-disubstituted vinylsilane linkage can be further elaborated through thiol-ene coupling or fluoride-induced protodesilylation, demonstrating its utility in further rounds of targeted modifications.

SUBMITTER: Kwan TT

PROVIDER: S-EPMC5578368 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

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Publications

Protein modification <i>via</i> alkyne hydrosilylation using a substoichiometric amount of ruthenium(ii) catalyst.

Kwan Terence T-L TT Boutureira Omar O Frye Elizabeth C EC Walsh Stephen J SJ Gupta Moni K MK Wallace Stephen S Wu Yuteng Y Zhang Fengzhi F Sore Hannah F HF Galloway Warren R J D WRJD Chin Jason W JW Welch Martin M Bernardes Gonçalo J L GJL Spring David R DR

Chemical science 20170314 5

Transition metal catalysis has emerged as a powerful strategy to expand synthetic flexibility of protein modification. Herein, we report a cationic Ru(ii) system that enables the first example of alkyne hydrosilylation between dimethylarylsilanes and <i>O</i>-propargyl-functionalized proteins using a substoichiometric amount or low-loading of Ru(ii) catalyst to achieve the first C-Si bond formation on full-length substrates. The reaction proceeds under physiological conditions at a rate comparab ...[more]

PMID: 28966779

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Project description:The only recently discovered gem-hydrogenation of internal alkynes is a fundamentally new transformation, in which both H atoms of dihydrogen are transferred to the same C atom of a triple bond while the other position transforms into a discrete metal carbene complex. [Cp*RuCl]4 is presently the catalyst of choice: the resulting piano-stool ruthenium carbenes can engage a tethered alkene into either cyclopropanation or metathesis, and a prototypical example of such a reactive intermediate with an olefin ligated to the ruthenium center has been isolated and characterized by X-ray diffraction. It is the substitution pattern of the olefin that determines whether metathesis or cyclopropanation takes place: a systematic survey using alkenes of largely different character in combination with a computational study of the mechanism at the local coupled cluster level of theory allowed the preparative results to be sorted and an intuitive model with predictive power to be proposed. This model links the course of the reaction to the polarization of the double bond as well as to the stability of the secondary carbene complex formed, if metathesis were to take place. The first application of "hydrogenative metathesis" to the total synthesis of sinularones E and F concurred with this interpretation and allowed the proposed structure of these marine natural products to be confirmed. During this synthesis, it was found that gem-hydrogenation also provides opportunities for C-H functionalization. Moreover, silylated alkynes are shown to participate well in hydrogenative metathesis, which opens a new entry into valuable allylsilane building blocks. Crystallographic evidence suggests that the polarized [Ru-Cl] bond of the catalyst interacts with the neighboring R3Si group. Since attractive interligand Cl/R3Si contacts had already previously been invoked to explain the outcome of various ruthenium-catalyzed reactions, including trans-hydrosilylation, the experimental confirmation provided herein has implications beyond the present case.

Dataset Information

Protein modification via alkyne hydrosilylation using a substoichiometric amount of ruthenium(ii) catalyst.

Publications

Protein modification <i>via</i> alkyne hydrosilylation using a substoichiometric amount of ruthenium(ii) catalyst.

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