Electrochemical Synthesis of Functional Aryl- and Heteroarylchlorosilanes. Application to the Preparation of Donor−Acceptor or Donor−Donor Organosilicon Molecules

Moreau, C.; Serein-Spirau, Françoise; Bordeau, and Michel; Biran, C.

doi:10.1021/om0009637

Cited by 14 publications

(30 citation statements)

References 33 publications

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“…765 As another application of nickel catalyzed electroreductive transformations of aryl halides, silylation of aryl bromides was reported. 766 …”

Section: Cathodic Reductionmentioning

confidence: 99%

“…765 As another application of nickel catalyzed electroreductive transformations of aryl halides, silylation of aryl bromides was reported. 766 Complexes of cobalt and pyridine exhibit similar reactivity with nickel in that they readily undergo cathodic reduction to generate low valent Co species which are capable of oxidative insertion into aryl C−X bonds. The resulting organocobalt complex can undergo transmetalation with zinc salts, offering an efficient means to prepare organozinc reagents (Figure 44G).…”

Section: Cathodic Generation Of Low Valent Nickel and Cobalt Species:...mentioning

confidence: 99%

“…Very recently, Hansen and co-workers reported an electrochemical method for the cross-electrophile coupling between aryl halides and unactivated alkyl halides . As another application of nickel catalyzed electroreductive transformations of aryl halides, silylation of aryl bromides was reported …”

Section: Cathodic Reductionmentioning

confidence: 99%

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Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

2017

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“…765 As another application of nickel catalyzed electroreductive transformations of aryl halides, silylation of aryl bromides was reported. 766 …”

Section: Cathodic Reductionmentioning

confidence: 99%

Section: Cathodic Generation Of Low Valent Nickel and Cobalt Species:...mentioning

confidence: 99%

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Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

2017

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“…The ramification is that even though the SiCl bond is reduced first, electroreduction of C‐Cl bonds to carbanions (eq 4 and 5, Scheme ) would be dominant. Another possible cause of preferential activation of CCl bonds involves the Ni(0)/TDA‐1 catalysis 30…”

Section: Resultsmentioning

confidence: 99%

Placement of radiopaque clips for tumor localization in patients undergoing neoadjuvant chemotherapy and breast conservation therapy

Nguyen

Whitman

et al. 2007

Cancer

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An electropolymerization of haloalkylhalosilanes (ClRSiCH3Cl2) that possess two types of electroactive sites, that is, the CCl and SiCl bond is described. The one‐pot synthesis method is shown to yield branched polycarbosilanes having a regular carbon block‐spaced silicon backbone structure. A series of branched polycarbosilanes, [RSiCH3]n with R being CH2, C2H4, C3H6, and CH2C6H4C2H4, have been successfully electropolymerized with Mn up to 42,600 Dalton. Experimental and simulation cyclic voltammetry of these monomers and the computational examination of their LUMOs are applied to study the electropolymerization mechanism. The results suggest that polymerization proceeds by iterating steps involving (1) electroreduction of a CCl bond to a carbanion, which is catalyzed by silylanion radical [Cl SiCl(CH3)RCl] and/or Ni(0)/TDA‐1; and (2) nucleophilic attack of carbanions to SiCl bonds of a second monomer or oligomer to extend the polymer chain. The investigation reveals that the R spacer has a considerable impact on the polymerizability of the corresponding monomer. Such interfacial polymerization resembles a template polymerization, leading to unique microstructures that were preserved even after converted to silicon carbide ceramics at high temperatures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7677–7689, 2008

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“…[14][15][16] They found that a large excess of chlorosilane, a strongly coordinating co-solvent (mostly hexamethyl phosphoric triamide HMPA) and/or a Ni catalyst, had to be used in order to preserve one of the chloro substituents on silicon (cf. Scheme 3).…”

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confidence: 99%

Electrochemical Synthesis of Functional Organosilanes II: Direct Electrochemical Formation of Si-C Bonds

Grogger

Loidl

Stueger

et al. 2013

J. Electrochem. Soc.

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Electroreductive Si-C bond formation was used for the formation of organofunctional silanes of the general formula HMe 2 Si-R-Y and MeOMe 2 Si-R-Y (R = alkylene, arylene; Y = H, MeO, Me 2 N, t-BuMe 2 SiO). Employing constant current conditions, different organic halides R-X (R = alkylene, arylene, X = Cl, Br) were electrolyzed in the presence of Me 2 Si(OMe) 2 and HMe 2 SiCl, respectively. All electrolyses were carried out in an undivided cell and with a THF/LiCl (MgCl 2 ) electrolyte. Although both salts are suitable supporting electrolytes, the highest conductivity was obtained with a mixture of LiCl/MgCl 2 = 2/1. It was shown that the reaction proceeds smoothly at current densities between 0.25 and 35 mA cm −2 . Cooling of the electrolysis cell can be omitted.There exist a variety of methods for silicon-carbon bond formation. Examples include the fundamental industrial Direct Process, Grignard-type processes, Wurtz-Fittig coupling reactions and transition metal-catalyzed reactions. 1 One practical method that can be utilized on the laboratory scale is the electrochemical formation of Si-C bonds, which basically involves the reduction of the organic substrate followed by an attack of the electrogenerated C-nucleophile on the Si-Cl bond of a chlorosilane (Scheme 1).In the early 1980s, Shono et al. 2,3 and Yoshida et al. 4 showed that this kind of electroreductive cross-coupling is possible in a divided cell with Pt anodes, but no defined anodic oxidation products were reported. In the great majority of the following papers reporting electrochemical Si-C bond formation, Me 3 SiCl was used as the silyl source. A variety of organic substrates was used with different experimental setups. [5][6][7][8] When di-, tri-or tetrachlorosilanes were used as the electrophiles in stoichiometric quantities, all chlorine substituents on silicon reacted with the electrochemically generated carbanions, thus yielding the corresponding linear, branched or cyclic Si-C compounds. 9-13 There are only a few examples demonstrating that functionality on the silicon atom can be retained: Yoshida et al. 4 reduced cinnamyl chloride in a divided cell with Pt electrodes in the presence of an excess of HMe 2 SiCl. They obtained a mixture of 1,1 and 1,3 silylation products, thus proving the stability of the Si-H bond under electrochemical conditions (Scheme 2).Bordeau et al. electrolyzed several aryl and heteroaryl bromides in the presence of dichlorosilanes R 2 SiCl 2 in an undivided cell with sacrificial anodes. 14-16 They found that a large excess of chlorosilane, a strongly coordinating co-solvent (mostly hexamethyl phosphoric triamide HMPA) and/or a Ni catalyst, had to be used in order to preserve one of the chloro substituents on silicon (cf. Scheme 3).We have been studying the synthesis of organofunctional silanes (OFS) of the general formula X-(Me 2 )Si-R-Y, where X and Y are reactive functional groups and R = alkylene or arylene. With potentially reactive substituents at both silicon and at carbon, these products are useful reactants i...

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Electrochemical Synthesis of Functional Aryl- and Heteroarylchlorosilanes. Application to the Preparation of Donor−Acceptor or Donor−Donor Organosilicon Molecules

Cited by 14 publications

References 33 publications

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Placement of radiopaque clips for tumor localization in patients undergoing neoadjuvant chemotherapy and breast conservation therapy

Electrochemical Synthesis of Functional Organosilanes II: Direct Electrochemical Formation of Si-C Bonds

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