New catalytic route to functionalized vinylboronates

Marciniec, Bogdan; Jankowska, Magdalena; Pietraszuk, Cezary

doi:10.1039/b414644a

Cited by 74 publications

(46 citation statements)

References 21 publications

(5 reference statements)

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“…Reactions of alkenes range from hydrogenation [11,12] and isomerization, [11,13] to diverse addition and coupling reactions. [14] In particular, Yis group has explored hydrovinylation [15,16] and dehydrogenative coupling of cyclic amines and alkenes, [17] and extensive studies by Marciniec and coworkers showcase the synthetic utility of 2 in silylative [14,18] and borylative [19] coupling, and related borylation [20] reactions. Triple bonds can also be activated: Beatty has reported that 2 functions as a precatalyst for the reductive hydrolysis of nitriles, [21] while Marciniecs group recently developed new catalytic routes to functionalized alkynylylsilanes and alkynylgermanes by using 2 to activate sp-hybridized carbon-hydrogen bonds.…”

Section: Introductionmentioning

confidence: 99%

Improved Syntheses of Versatile Ruthenium Hydridocarbonyl Catalysts Containing Electron‐Rich Ancillary Ligands

et al. 2008

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Section: Introductionmentioning

confidence: 99%

Improved Syntheses of Versatile Ruthenium Hydridocarbonyl Catalysts Containing Electron‐Rich Ancillary Ligands

et al. 2008

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“…Vinylboronic acids can be easily synthesized as the protected ester in one step by,f or example,c rossmetathesis between an alkene and av inylboronic ester [12] or hydroboration of an alkyne. [13] Hydrolysis of the boronic ester occurs spontaneously in aqueous media, although many deprotection strategies to the boronic acid are also available.…”

Section: Zuschriftenmentioning

confidence: 99%

Vinylboronic Acids as Fast Reacting, Synthetically Accessible, and Stable Bioorthogonal Reactants in the Carboni–Lindsey Reaction

Eising¹,

Lelivelt²,

Bonger³

2016

Angewandte Chemie

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Bioorthogonal reactions are widely used for the chemical modification of biomolecules.T he application of vinylboronic acids (VBAs) as non-strained, synthetically accessible and water-soluble reaction partners in ab ioorthogonal inverse electron-demand Diels-Alder (iEDDA) reaction with 3,6-dipyridyl-s-tetrazines is described. Depending on the substituents,VBA derivatives give second-order rate constants up to 27 m À1 s À1 in aqueous environments at room temperature, which is suitable for biological labeling applications.T he VBAs are shown to be biocompatible,n on-toxic, and highly stable in aqueous media and cell lysate.F urthermore,V BAs can be used orthogonally to the strain-promoted alkyne-azide cycloaddition for protein modification, making them attractive complements to the bioorthogonal molecular toolbox.Inthe last decades,t he development of selective reactions between two reactants that are unaffected by any of the naturally occurring biological functionalities has been amajor research area in chemical biology.[1] These bioorthogonal reactions ( Figure 1A)m ake it possible to chemically modify biomolecules in their native cellular environment and gain ab etter understanding of their role in as pecific biological system or process.The bioorthogonal reaction should be high yielding and rapid, and the reactants and product(s) should be soluble and stable in aqueous media and non-toxic to the biological system. Theu se of small reactants is preferred to minimize steric interactions with the biomolecule or to facilitate incorporation by the endogenous cellular machinery.TheCarboni-Lindsey (CL) reaction between an electronpoor tetrazine ( Figure 1B, I)a nd an alkene has gained considerable attention for use in bioorthogonal applications. [2] As linear and unmodified alkenes ( Figure 1B, VI)s howed only poor reaction rates with tetrazines, [3] most research has been directed to the development and use of strained alkenes such as trans-cyclooctene (TCO), [4] norbornene, [5] cyclopropene, [6] or N-acylazetine [7] ( Figure 1B, II-V). In addition to strain, the rate of the CL reaction can be significantly enhanced by the introduction of electron-donating substituents on the alkene bond.[8] This aspect, however,h as been poorly investigated in relation to bioorthogonal applications.Vinylboronic acids ( Figure 1B, VII)a re an interesting class of compounds with unique electronic properties,w hich are due to their vacant p-orbital. As aresult of the inductive effect that is caused by the electronegativity difference of boron and carbon, the electronic deficiencyofboron and the electron-donating oxygens attached to boron, boronic acid is considered to be aw eak electron-donor.[9] Furthermore, boronic acids are mild organic Lewis acids,w hich in basic aqueous media are in equilibrium with their boronate anion ( Figure 1B, VIII), which is as trong electron-donor. [9] Although Diels-Alder reactions are known to proceed faster in aqueous media, the CL reactions of vinylboronic acids and alkylboronic acids are re...

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“…Similarly to the previously described trans-metalation reactions of vinylmetalloid with olefins and acetylenes [2][3][4][5] (for a review see ref.…”

Section: Resultsmentioning

confidence: 87%

“…Although vinylborane has to be used in excess, its homocoupling [3] has been practically insignificant in this reaction. On the other hand, dimerisation of acetylene has been observed, but in the presence of most catalysts used, only as a side reaction affording traces of byproducts (c).…”

Section: Resultsmentioning

confidence: 98%

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A New Catalytic Route to Boryl‐ and Borylsilyl‐Substituted Buta‐1,3‐dienes

Walkowiak

Jankowska‐Wajda

Marciniec

2008

Chemistry A European J

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Vinyl-substituted boronates in the presence of complexes containing Ru-H bonds (preferably [Ru(CO)ClH(PCy(3))(2)], Cy: cyclohexyl) react regioselectively with terminal ethynes (involving silylethynes), albeit with the exception of phenylacetylene, to produce boryl- and borylsilyl-substituted buta-1,3-dienes with a preference for E,E-diene. The reaction opens a new catalytic route for the preparation of dienylboronates, and particularly dienylsilylboronates, that are functionalised building blocks in the synthesis of organic and natural products. The mechanism of this new reaction was proved to involve an insertion of alkyne into Ru-H bonds followed by an insertion of coordinated vinyl boronate into the Ru-C= bond and beta-hydrogen transfer to the metal to eliminate boryldiene or borylsilyldiene.

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New catalytic route to functionalized vinylboronates

Abstract: Vinylsubstituted boronates i.e. vinyldioxaborolane and vinyldioxaborinane react regioselectively with olefins in the presence of RuHCl(CO)(PCy3)2 with the formation of functionalized vinylboron derivatives. The reaction opens a new catalytic route for preparation of organoboranes.

Cited by 74 publications

References 21 publications

Improved Syntheses of Versatile Ruthenium Hydridocarbonyl Catalysts Containing Electron‐Rich Ancillary Ligands

Improved Syntheses of Versatile Ruthenium Hydridocarbonyl Catalysts Containing Electron‐Rich Ancillary Ligands

Vinylboronic Acids as Fast Reacting, Synthetically Accessible, and Stable Bioorthogonal Reactants in the Carboni–Lindsey Reaction

A New Catalytic Route to Boryl‐ and Borylsilyl‐Substituted Buta‐1,3‐dienes

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