64788-84-7

Upstream product

• 588-73-8 (Z)-β-bromostyrene 
• 79628-15-2 dimethyl(phenyl)(phenylethynyl)silane 
• 766-77-8 Dimethylphenylsilane 
• 536-74-3 phenylacetylene 
• 100-52-7 benzaldehyde 
• 270589-07-6 2-pyridyldimethyl[(phenyldimethylsilyl)methyl]silane 
• 100-42-5 styrene 
• 768-33-2 phenyldimethylsilyl chloride 

Downstream Products

• 3783-65-1 (E)-2-(2-phenylethenyl)thiophene 
• 1694-19-5 E-1-(phenyl)-2-(4'-methoxyphenyl)ethene 
• 1896-62-4 (E)-benzalacetone 
• 1186072-06-9 dimethyl(phenyl)[(2R,3S)-3-phenyloxiran-2-yl]silane 
• 1186072-16-1 dimethyl(phenyl)[(2S,3R)-3-phenyloxiran-2-yl]silane 
• 64788-85-8 dimethyl-phenyl-((E)-styryl)-silane 

Relevant academic research and scientific papers

Stereocontrolled synthesis of (E)- and (Z)-poly(p-phenylenevinylene)s via ruthenium-catalyzed hydrosilylation of p-diethynylbenzene

Stereocontrolled synthesis of poly(phenylenevinylene)s (PPVs) with (E)- and (Z)-vinylene units has been examined. Ruthenium complex-catalyzed hydrosilylation of p-diethynylbenzene with HSiMe2Ar (Ar=2-thienyl (Th),3,5-(CF3)2C6H3) proceeds readily in CH2Cl2 at room temperature to give (E,E)- or (Z,Z)-bis(2-silylethenyl)benzenes (3a, 3b) in 89-40% yields. The geometries of 3a and 3b are clearly dependent on ruthenium catalysts employed. Thus, RuHCl(CO)(PPh3)3 forms (E,E)-isomers in over 99% selectivities, whereas RuCl2(CO) (PPri3)2 affords (Z,Z)-3a and 3b with 92 and 91% geometrical purities, respectively. The (E,E)- and (Z,Z)-isomers of 3a and 3b undergo polycondensation with 2,5-dioctyloxy-1,4-diiodobenzene in THF in the presence of a palladium catalyst ([PdCl(η3-allyl)]2, Pd(dba)2) and tetrabutylammonium fluoride hydrate, giving (E)-rich and (Z)-rich PPVs in high yields.

The two faces of platinum hydrospirophosphorane complexes—Not only relevant catalysts but cytotoxic compounds as well

Platinum complexes [PtCl2(L)] L = L1, L2 with symmetrical HP (OCH2CMe2NH)2 (L1) and unsymmetrical HP(OCMe2CMe2O)(OCH2CMe2NH) (L2) hydrospirophosphorane (HSP) ligands were demonstrated to play a dual role of catalysts and cytotoxic compounds as well. The structure of new complex [PtCl2(L2)] was confirmed by physicochemical and spectroscopic methods, as well as single X-ray diffraction studies for [PtCl2{P (OCMe2CMe2O)(OCH2CMe2NH2)}]. HSP ligand coordinated to the platinum center in bidentate κ2-P,NH2 chelating mode of fashion. Both complexes were found to exhibit catalytic activity for Heck cross-coupling reactions of iodobenzene with substituted styrenes, with good conversion and yield of stilbenes. Moreover, complexes have been applied as excellent catalysts for highly regioselective hydrosilylation of aromatic and aliphatic terminal olefins, and acetylenes terminal and internal as well. On the other hand, the preliminary biological studies revealed that in the presence of foretinib, drug candidate in clinical trials for the treatment of cancer, platinum complexes revealed increased synergistic effect and efficiently decreased the number of viable cells of triple negative breast cancer MDA-MB-231 cell line.

Caged Iridium Catalyst for Hydrosilylation of Alkynes with High Site Selectivity

The proximity and orientation of the reacting groups can be different in organic cages from in free solution, thus affecting the selectivity of the reaction. Herein, we reported a synthetic strategy to encapsulate iridium nanoparticles (Ir-NP@COP1-T) within organic cages in the homogeneous solution. Ir-NP@COP1-T showed good selectivity in the hydrosilylation reaction of alkynes. Our work provides a new perspective to the catalysis field by using soluble microporous cages as support for inorganic nano particles.

Ruthenium-catalyzed hydrosilylation of alkynes with preservation of the Si–Si bond of hydrooligosilanes: Regio- and stereoselective synthesis of (Z)-alkenyloligosilanes and carbonyl-functionalized alkenyldisilanes

Ruthenium-catalyzed Z-selective hydrosilylation of alkynes afforded alkenyloligosilanes with high regio- and stereoselectivity without Si–Si bond cleavage. Among examined catalysts, RuHCl(CO)(PPh3)(dppp) was found to be the most suitable for the Z-selective hydrosilylation. A deuterium labeling experiment suggests the existence of a vinylideneruthenium species which is the key intermediate for the Z-selectivity. By using this method as well as previously reported E- and α-selective hydrosilylation, (E)-, (Z)- and α-alkenyldisilanes bearing carbonyl functionality were selectively synthesized.

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.

Iridium(i) complexes bearing hemilabile coumarin-functionalised N-heterocyclic carbene ligands with application as alkyne hydrosilylation catalysts

A set of iridium(i) complexes of formula IrCl(κC,η2-IRCouR′)(cod) or IrCl(κC, η2-BzIRCouR′)(cod) (cod = 1,5-cyclooctadiene; Cou = coumarin; I = imidazolin-2-carbene; BzI = benzimidazolin-2-carbene) have beeen prepared from the corresponding azolium salt and [Ir(μ-OMe)(cod)]2 in THF at room temperature. The crystalline structures of 4b and 5b show a distorted trigonal bipyramidal configuration in the solid state with a coordinated coumarin moiety. In contrast, an equilibrium between this pentacoordinated structure and the related square planar isomer is observed in solution as a consequence of the hemilability of the pyrone ring. Characterization of both species by NMR was achieved at the low and high temperature limits, respectively. In addition, the thermodynamic parameters of the equilibrium, ΔHR and ΔSR, were obtained by VT 1H NMR spectroscopy and fall in the range 22-33 kJ mol-1 and 72-113 J mol-1 K-1, respectively. Carbonylation of IrCl(κC,η2-BzITolCou7,8-Me2)(cod) resulted in the formation of a bis-CO derivative showing no hemilabile behaviour. The newly synthesised complexes efficiently catalyze the hydrosilylation of alkynes at room temperature with a preference for the β-(Z) vinylsilane isomer.

Rh(I)/(III)-N-Heterocyclic Carbene Complexes: Effect of Steric Confinement Upon Immobilization on Regio- and Stereoselectivity in the Hydrosilylation of Alkynes

Rh(I) NHC and Rh(III) Cp* NHC complexes (Cp=pentamethylcyclopentadienyl, NHC=N-heterocyclic carbene=pyrid-2-ylimidazol-2-ylidene (Py?Im), thiophen-2-ylimidazol-2-ylidene) are presented. Selected catalysts were selectively immobilized inside the mesopores

Carboxylate-Assisted β-(Z) Stereoselective Hydrosilylation of Terminal Alkynes Catalyzed by a Zwitterionic Bis-NHC Rhodium(III) Complex

The zwitterionic compound [Cp*RhCl{(MeIm)2CHCOO}] is an efficient catalyst for the hydrosilylation of terminal alkynes with excellent regio- and stereoselectivity toward the less thermodynamically stable β-(Z)-vinylsilane isomer under mild reaction conditions. A broad range of linear 1-alkynes, cycloalkyl acetylenes, and aromatic alkynes undergo the hydrosilylation with HSiMe2Ph to afford the corresponding β-(Z)-vinylsilanes in quantitative yields in short reaction times. The reaction of aliphatic alkynes with HSiEt3 is slower, resulting in a slight decrease of selectivity toward the β-(Z)-vinylsilane product, which is still greater than 90%. However, a significant selectivity decrease is observed in the hydrosilylation of aromatic alkynes because of the β-(Z) → β-(E) vinylsilane isomerization. Moreover, the hydrosilylation of bulky alkynes, such as t-Bu-CCH or Et3SiCCH, is unselective. Experimental evidence suggests that the carboxylate function plays a key role in the reaction mechanism, which has been validated by means of density functional theory calculations, as well as by mass spectrometry and labeling studies. On the basis of previous results, we propose an ionic outer-sphere mechanism pathway in which the carboxylate fragment acts as a silyl carrier. Namely, the hydrosilylation mechanism entails the heterolytic activation of the hydrosilane assisted by the carboxylate function to give the hydrido intermediate [Cp*RhH{(MeIm)2CHCOO-SiR3}]+. The transference of the silylium moiety from the carboxylate to the alkyne results in the formation of a flat β-silyl carbocation intermediate that undergoes a hydride transfer from the Rh(III) center to generate the vinylsilane product. The outstanding β-(Z) selectivity results from the minimization of the steric interaction between the silyl moiety and the ligand system in the hydride transfer transition state.

β-(Z) Selectivity Control by Cyclometalated Rhodium(III)-Triazolylidene Homogeneous and Heterogeneous Terminal Alkyne Hydrosilylation Catalysts

The cyclometalated Rh(III)-NHC compounds [Cp*RhI(C,C′)-Triaz] (Triaz = 1,4-diphenyl-3-methyl-1,2,3-triazol-5-ylidene) and [Cp*RhI(C,C′)-Im] (Im = 1-phenyl-3-methyl-imidazol-2-ylidene) are efficient catalysts for the hydrosilylation of terminal alkynes wit

Visible-Light-Initiated Manganese-Catalyzed E-Selective Hydrosilylation and Hydrogermylation of Alkynes

Manganese-photocatalyzed activation of the Si-H bond in silanes for the hydrosilylation of alkynes has been developed. The mild protocol operates efficiently with high regioselectivity (anti-Markovnikov) and stereoselectivity (Z/E ratio ranges from 92:8 to >99:1), providing a wide range of Z-vinylsilanes in high yields. Moreover, visible-light-induced manganese-catalyzed activation of the Ge-H bond for E-selective alkyne hydrogermylation is reported for the first time.