63522-98-5

Upstream product

• 617-86-7 triethylsilane 
• 300-57-2 allylbenzene 
• 637-50-3 1-phenylpropene 
• 994-30-9 triethylsilyl chloride 
• 16519-25-8 (E)-cinnamyl phenyl ether 
• 138621-80-4 1-phenyl-1-phenoxy-2-propene 
• 2327-99-3 1-phenylpropadiene 
• 693-04-9 butyl magnesium bromide 
• 15366-08-2 s-butylmagnesium chloride 
• 677-22-5 tert-butylmagnesium chloride 
• 745783-97-5 triethyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 536-74-3 phenylacetylene 

Relevant academic research and scientific papers

Silylation and alkylation of allenes using chlorosilanes and alkyl halides in the presence of palladium catalyst and Grignard reagents

Allenes react with Grignard reagents and chlorosilanes in the presence of a palladium catalyst giving rise to carbosilylated products bearing carbon groups from Grignard reagents at the central carbon and silyl groups at the terminal carbon. When alkyl halides were used instead of chlorosilanes, the corresponding alkylated products were obtained.

Manganese-catalysed divergent silylation of alkenes

Transition-metal-catalysed, redox-neutral dehydrosilylation of alkenes is a long-standing challenge in organic synthesis, with current methods suffering from low selectivity and narrow scope. In this study, we report a general and simple method for the manganese-catalysed dehydrosilylation and hydrosilylation of alkenes, with Mn2(CO)10 as a catalyst precursor, by using a ligand-tuned metalloradical reactivity strategy. This enables versatility and controllable selectivity with a 1:1 ratio of alkenes and silanes, and the synthetic robustness and practicality of this method are demonstrated using complex alkenes and light olefins. The selectivity of the reaction has been studied using density functional theory calculations, showing the use of an iPrPNP ligand to favour dehydrosilylation, while a JackiePhos ligand favours hydrosilylation. The reaction is redox-neutral and atom-economical, exhibits a broad substrate scope and excellent functional group tolerance, and is suitable for various synthetic applications on a gram scale. [Figure not available: see fulltext.].

Manganese-Catalyzed Dehydrogenative Silylation of Alkenes following Two Parallel Inner-Sphere Pathways

We report on an additive-free Mn(I)-catalyzed dehydrogenative silylation of terminal alkenes. The most active precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe)(CO)3(CH2CH2CH3)]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate which undergoes rapid Si-H bond cleavage of the silane HSiR3 forming the active 16e- Mn(I) silyl catalyst [Mn(dippe)(CO)2(SiR3)] together with liberated butanal. A broad variety of aromatic and aliphatic alkenes was efficiently and selectively converted into E-vinylsilanes and allylsilanes, respectively, at room temperature. Mechanistic insights are provided based on experimental data and DFT calculations revealing that two parallel reaction pathways are operative: an acceptorless reaction pathway involving dihydrogen release and a pathway requiring an alkene as sacrificial hydrogen acceptor.

Manganese catalyzed dehydrogenative silylation of alkenes: Direct access to allylsilanes

Dehydrogenative silylation of alkenes with silanes to produce allylsilanes is achieved through manganese catalysis with a wide scope of substrate tolerance. This transformation involves silane radicals initiated by manganese complex without additional oxidant additives. It offers a general, convenient and practical protocol with excellent functional group compatibility and gram-scale capacity for the modular synthesis of allylsilanes.

Ligand-Controlled Regiodivergent Silylation of Allylic Alcohols by Ni/Cu Catalysis for the Synthesis of Functionalized Allylsilanes

The first Ni/Cu-catalyzed regiodivergent synthesis of allylsilanes directly from allylic alcohols through modulating the steric and electronic properties of the ligands on the nickel catalyst has been developed. Good yields and excellent selectivity were obtained regardless of whether linear or α-branched allylic alcohols were utilized. Mechanistic studies indicate that an allyloxyboronate species is formed during the reaction, which likely serves as an activated intermediate toward the oxidative addition of the C(allyl)-O bond.

Synthesis and behavior of novel sulfonated water-soluble N-heterocyclic carbene (η4-diene) platinum(0) complexes

A series of water-soluble (NHC)Pt(0)(dvtms) and (NHC)Pt(0)(AE) complexes containing different sulfonated NHC ligands (dvtms = divinyltetramethyldisiloxane and AE = diallyl ether) are reported. The dvtms compounds have been found to be quite robust and to display some conformational rigidity, whereas their AE counterparts are less stable and more flexible. The catalytic evaluation of these complexes in the hydrosilylation of alkynes in water revealed no benefits in favor of the complexes containing the more labile spectator diene (AE), and a fairly regular catalytic behavior for all complexes that restricts the location of the sulfonate group to the proximity of the metal site.

Rhodium(II)-catalyzed stereoselective synthesis of allylsilanes

The rhodium-catalyzed decomposition of 2-(triisopropylsilyl)ethyl aryl- and vinyldiazoacetates results in the stereoselective formation of Z-allylsilanes. The transformation is considered to proceed by silyl-directed intramolecular C-H functionalization to form a β-lactone intermediate followed by a silyl-activated extrusion of carbon dioxide.

Titanocene-catalyzed formation of allylsilanes from allyl ethers and chlorosilanes

A new method for silylation of allyl ethers with chlorosilanes has been developed by the use of Cp2TiCl2 as a catalyst. This reaction proceeds efficiently at -20°C in THF using nBuMgCl. A plausible reaction pathway via allyltitanocene intermediate was proposed.

Reaction pathways of zirconocene-catalyzed silylation of alkenes with chlorosilanes

Reaction pathways as well as stereochemistries and stoichiometries of zirconocene-catalyzed silylation of olefins with chlorosilanes in the presence of nBuMgCl were studied and discussed in detail. Rate determining steps were examined by kineti

Zirconocene-catalyzed silylation of alkenes with chlorosilanes

Vinylsilanes and/or allylsilanes are formed upon silylation of terminal alkenes with R3SiCl in the presence of a Grignard reagent and a catalytic amount of [Cp2ZrCl2] [Eq. (a)]. The reaction also proceeds under mild condit