Copper-catalyzed Hiyama cross-coupling using vinylsilanes and benzylic electrophiles

Cornelissen, Loïc; Cirriez, Virginie; Vercruysse, Sébastien; Riant, Olivier

doi:10.1039/c4cc02923b

Cited by 34 publications

(18 citation statements)

References 23 publications

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“…The reaction tolerates a variety of functional groups on alkyl halides including highly sensitive esters ( Table 2 , entries, 5, 9 and 11), nitriles ( Table 2 , entries 6 and 7) and olefins ( Table 2 , entries 4, 8, 10, 13 and 15) [ 46 ]. With 10 mol % catalyst loading, the reaction can also be extended to the coupling of triarylaluminum reagents with benzyl bromides ( Table 2 , entries 12 and 14) [ 43 ].…”

Section: Resultsmentioning

confidence: 99%

“…Triorganoaluminum complexes are also known to form triorganoaluminate species in the presence of anions in solution [ 52 – 57 ]. In addition, organoaluminum reagents have been demonstrated to undergo transmetalation with Cu salts based on their participation in allylic and conjugate addition reactions [ 11 , 15 , 43 ]. Similar Cu-catalyzed couplings of organometallic reagents with alkyl electrophiles have previously been shown to proceed via an S N 2 process [ 34 – 35 ].…”

Section: Resultsmentioning

confidence: 99%

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Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

Shrestha¹,

Giri²

2015

Beilstein J. Org. Chem.

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SummaryWe report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

Shrestha¹,

Giri²

2015

Beilstein J. Org. Chem.

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“…Thus, this copper‐catalyzed protocol was shown to effectively overcome the substrate scope limitation for the carboxylation of arylsilanes observed in previous literature reports. In addition to arylsilanes, the carboxylation of alkenylsilane 1 i , which was easily obtained from the platinum‐catalyzed hydrosilylation of phenylacetylene,, afforded cinnamic acid ( 4 i ) in a good yield (Scheme ).…”

Section: Figurementioning

confidence: 99%

Copper‐Catalyzed Carboxylation of Aryl‐ and Alkenyltrialkoxysilanes

2017

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The use of as imple coppers alt as ac atalyst, in conjunction with CsF as an activator, enabled aw ide range of aryl-and alkenyltrialkoxysilanes to undergo carboxylation under atmosphericp ressure of CO 2 ,a ffording the corresponding carboxylic acids in good to high yields.Since carbon dioxide (CO 2 )i sa na bundant, clean, and renewable C1 feedstock, its use in organic synthesis is attractive and complies with the principles of green and sustainable chemistry.[1] In general, CO 2 is weakly electrophilic and is known to react with organometallic nucleophiles to afford carboxylic acids and its derivatives. While typically strongo rganometallic nucleophiles, such as organolithiums and Grignard reagents, are known to react readily with CO 2 ,t heir sensitivity to moisture and poor functional group compatibilitym akes these reagents unattractive.T oo vercome these problems, recent advancesi nt his field focusedo nc atalyzed carboxylation reactions of more stable and less sensitive reagents, including organozincs, [2] organoaluminums, [3] organoborons, [4] and organosilicons.[5] In particular,t he carboxylation of arylboronic esters has been well-studiedw ith various transition metal catalysts (Rh, Cu, Ag, Ni), and broad substrate scope and high functional group tolerance wereo bserved in all cases.[4a-e] On the other hand, the carboxylation of arylsilanes has been less explored with limited success, [5e-h] despite the fact that they are competent nucleophilic partnersi nvariousc ross-coupling reactions. [6] Previously reported resultsb yE ffenberger [5e] and Sato [5f] demonstrated that arylsilanes bearing electron-deficient substituents at the ortho positions could smoothly react with CO 2 in the presence of af luoridea nion source. In their hypothesis, the electron-withdrawing moiety stabilizes the aryl carbanions that were generated from the fluoride-mediated desilylation process. More recently,C antat achieved the carboxylation of heteroarylsilanes, in which the silicon moietyw as positioned ortho to the heteroatoms. [5g] In an attempt to develop am ore general carboxylation method, Kondo utilized phosphazenium salts as catalysts.[5h] Althought he presence of ortho substituents was avoided, their method was stilllimited to electron-deficienta rylsilanes. Based on these literature reports, it was clear that there were no efficient procedures to convert electronrich and neutral arylsilanes to carboxylic acids via carboxylation reactionswith CO 2 .To overcome the substrate scope limitation for the carboxylation of arylsilanes, we took inspiration from the richh istory of cross-couplingr eactions involving arylsilanes,a nd considered the use of copper salts as catalysts (Figure 1). In our working hypothesis, after the formationo ft he pentavalent silicate via fluoride activation, the transmetallationo ft his activated speciesw ith ac opper catalystw ould generate an arylcopper intermediate that could readily react with CO 2 to generate the desired carboxylic acid. The transmetallation of hypervale...

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“…The same type of benzyl bromides 68 were coupled with the vinylsilane 70 under copper catalysis in the presence of tetrabutylammonium difluorotriphenylsilicate (TBAT) to afford the corresponding products 71 (Scheme ) 57…”

Section: Alkenylation Reactionsmentioning

confidence: 99%

The Hiyama Cross‐Coupling Reaction: New Discoveries

Foubelo

Nájera

Yus

2016

The Chemical Record

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ABSTRACT:In this review article recent developments in the Hiyama cross-coupling reaction from 2010 up today are presented. The most important methodology involves formation of biaryl systems by using aryl bromides or iodides and aryl trialkoxy silanes: other variants are far less studied. The most useful procedures are collected paying special attention to the synthetic application of this methodology in synthetic organic chemistry.

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Copper-catalyzed Hiyama cross-coupling using vinylsilanes and benzylic electrophiles

Cited by 34 publications

References 23 publications

Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

Copper‐Catalyzed Carboxylation of Aryl‐ and Alkenyltrialkoxysilanes

The Hiyama Cross‐Coupling Reaction: New Discoveries

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