Synthesis of Functionalized 1‐Substituted Alkenylsilanols and Establishment of Conditions for Their Palladium‐Catalyzed Cross‐Coupling Reactions To Afford 1‐Substituted Styrene Derivatives

Ghosh, Sunil K.; Singh, Rekha; Singh, Gobind C.

doi:10.1002/ejoc.200400339

Cited by 17 publications

(12 citation statements)

References 70 publications

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“…In our initial crosscoupling studies, the reaction of 9a (either pure or generated in situ) with iodobenzene was carried out under the conventional Heck conditions using Pd(OAc) 2 /(o-Tol) 3 P in the presence or absence of TBAF at 80°C. The reaction was extremely slow with a conversion of Ͻ5 % in both the cases even after 40 h. We next choose [Pd(allyl)Cl] 2 as the catalyst because of our previous [15] success with it in ipso cross-coupling reactions. Reaction of the silanes 5a/6a with iodobenzene (1.5 equiv.…”

Section: Optimization Of Heck Reaction Conditionsmentioning

confidence: 99%

“…Our exploratory studies [15] on this cross-coupling reaction of a mixture of silanol 5a and disiloxane 6a with iodobenzene using [Pd(allyl)Cl] 2 as the catalyst and tetrabutylammonium fluoride (TBAF) or a combination of TBAF and tetrabutylammonium hydroxide (TBAOH) [20] as the promoter in various solvents gave a mixture of ipso-coupled 1-substituted styrene 8a, vinylated malonate 9a, formed due to protiodesilylation of silanes and the cine-coupled styrene derivative 10a (Scheme 3). Scheme 2.…”

Section: Heck Reaction Of Vinylated Malonates With Iodoarenesmentioning

confidence: 99%

“…possibility for the synthesis of this type of functionalized disiloxanes. For this, silylidene malonate 11 was subjected to our alkenyl silanol preparation conditions [15] using CF 3 SO 3 H, which exclusively gave disiloxane 16 in nearly quantitative yield. Disiloxane 16 underwent a smooth dimethylsulfonium methylide mediated double olefination (Me 3 SI + nBuLi) followed by double alkylation with benzyl bromide 12 in the same pot (Scheme 8) to give desired alkenyl disiloxane 6d in very good yield.…”

Section: Heck Reaction Leading To 14-diaryl-1-butenesmentioning

confidence: 99%

“…In a recent publication, we reported [15] a general method for the preparation of 1-substituted alkenylsilanols 5/disiloxanes 6 from the corresponding alkenyl(phenyl)silanes 7 [16] (Scheme 2) and their application in Hiyama-Denmarktype [17][18][19][20] cross-coupling reactions with iodoarenes. Our exploratory studies [15] on this cross-coupling reaction of a mixture of silanol 5a and disiloxane 6a with iodobenzene using [Pd(allyl)Cl] 2 as the catalyst and tetrabutylammonium fluoride (TBAF) or a combination of TBAF and tetrabutylammonium hydroxide (TBAOH) [20] as the promoter in various solvents gave a mixture of ipso-coupled 1-substituted styrene 8a, vinylated malonate 9a, formed due to protiodesilylation of silanes and the cine-coupled styrene derivative 10a (Scheme 3).…”

Section: Heck Reaction Of Vinylated Malonates With Iodoarenesmentioning

confidence: 99%

“…In this context, we prepared the required benzylated silanol/disiloxanes 5b,c/6b,c following our earlier described procedure [15] from alkenyl(phenyl)silanes 7b,c [16] by using trifluoromethanesulfonic acid as shown in Scheme 4.…”

Section: Heck Reaction Leading To 14-diaryl-1-butenesmentioning

confidence: 99%

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A Novel Approach Towards Dibenzylbutyrolactone Lignans Involving Heck and Radical Reactions: Application to (±)‐Matairesinol Synthesis

Singh

Ghosh

2007

Eur J Org Chem

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Section: Optimization Of Heck Reaction Conditionsmentioning

confidence: 99%

Section: Heck Reaction Of Vinylated Malonates With Iodoarenesmentioning

confidence: 99%

Section: Heck Reaction Leading To 14-diaryl-1-butenesmentioning

confidence: 99%

Section: Heck Reaction Of Vinylated Malonates With Iodoarenesmentioning

confidence: 99%

Section: Heck Reaction Leading To 14-diaryl-1-butenesmentioning

confidence: 99%

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A Novel Approach Towards Dibenzylbutyrolactone Lignans Involving Heck and Radical Reactions: Application to (±)‐Matairesinol Synthesis

Singh

Ghosh

2007

Eur J Org Chem

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β‐Silylmethylene Malonate as Versatile Reagent in Organic Synthesis

Ghosh

2022

Asian J Org Chem

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Copper(I)‐Catalyzed Highly Regio‐ and Stereoselective Hydrosilylation of Terminal Alkynes with Boryldisiloxane

Zhou

Wang

2014

ChemCatChem

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By employing 1,1,3,3-tetramethyl-1,3-(pinacolboryl)disiloxane as a novel silicon source, the N-heterocyclic carbene copper complex catalyzed hydrosilylation of terminal alkynes was developed to prepare vinyldisiloxanes in a highly regio-and stereoselective manner. A number of functional groups, including ether, ester, cyano, nitro, halo, hydroxyl, cyclopropyl, and aryl groups, were tolerated under the optimized conditions. A mechanistic investigation was undertaken by using density functional theory calculations. This approach allows facile entry to unsymmetrical disubstituted (E)-alkenes by Pd-catalyzed cross-coupling reactions.Vinylsilanes are versatile building blocks in organic synthesis [1] because of their extensive applications in protodesilylations, [2] Tamao-Fleming oxidations, [3] Hiyama-Denmark cross-coupling reactions, [4] and other transformations. [5] Although numerous successful catalytic processes, such as the hydrosilylation of alkynes with SiÀH reagents, [6] have been described to access these types of compounds, efforts to increase the catalytic activity and to control reaction selectivity with high substrate tolerance continue.Silylcupration [7] of carbon-carbon triple bonds followed by protonation is one of the most attractive routes to generate vinylsilanes with complete syn stereoselectivity. However, stoichiometric amounts of Fleming's silyl cuprate reagents (CuÀSi) by employing silyl-lithium (SiÀLi) [8] or silyl-stannane (SiÀSn) [9] reagents as the silicon sources are needed for this transformation. Recently, much attention has been directed toward the catalytic formation of functionalized vinylsilanes under copper catalysis, in which the key CuÀSi species arise from activation of disilane (SiÀSi) [10] or silylborane (SiÀB) reagents [11][12][13][14] (Scheme 1). The first copper(I)-catalyzed system for the hydrosilylation of alkynes conjugated to carbonyl groups was reported by Molander's group, who used diphenyltetramethyldisilane to obtain b-silyl-a,b-unsaturated carbonyl mixtures with different E/Z ratios in moderate yields.[10] Me 2 PhSiB(pin) (pin = pinacolato), an important silylborane (SiÀB) reagent owing to its versatile synthetic transformations, has been widely researched to effectively synthesize silicon-and/or boron-functionalized synthons.[15] Loh [11] reported that by using Me 2 PhSiB(pin) as the silicon source, CuCl bearing a phosphine ligand catalyzed the hydrosilylation of terminal alkynes to selectively form a-vinylsilanes, in which the hydrogen atom was provided by added alcohols. Unfortunately, the regioselectivity was decreased with the use of electron-deficient substrates. Very recently, N-heterocyclic carbene (NHC)-copper(I) complexes were found to be more efficient catalytic systems for the above reaction, and they afforded b-(E)-vinylsilanes with high regio-and stereoselectivity (> 98 % E and b).[12] During the preparation of this manuscript, Calderone and Santos [13] and Lipshutz [14] successively reported the copper-catalyzed hydrosilylation of electro...

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Synthesis of Functionalized 1‐Substituted Alkenylsilanols and Establishment of Conditions for Their Palladium‐Catalyzed Cross‐Coupling Reactions To Afford 1‐Substituted Styrene Derivatives

Abstract: An efficient method for the quantitative conversion of 1-substituted alkenyl(phenyl)silanes into the corresponding alkenylsilanols has been developed and used in their palladium(0)-catalyzed, tetrabutylammonium fluoride-promoted cross-coupling reaction with aryl iodides. Copper(I) chloride

Cited by 17 publications

References 70 publications

A Novel Approach Towards Dibenzylbutyrolactone Lignans Involving Heck and Radical Reactions: Application to (±)‐Matairesinol Synthesis

A Novel Approach Towards Dibenzylbutyrolactone Lignans Involving Heck and Radical Reactions: Application to (±)‐Matairesinol Synthesis

β‐Silylmethylene Malonate as Versatile Reagent in Organic Synthesis

Copper(I)‐Catalyzed Highly Regio‐ and Stereoselective Hydrosilylation of Terminal Alkynes with Boryldisiloxane

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