105281-54-7

Upstream product

• 529-28-2 4-iodoanisol 
• 754-05-2 ethenyltrimethylsilane 
• 40230-91-9 [(2-methoxyphenyl)ethynyl]trimethylsilane 
• 617-86-7 triethylsilane 
• 767-91-9 1-ethynyl-2-methoxybenzene 
• 18107-18-1 diazomethyl-trimethyl-silane 

Relevant academic research and scientific papers

Synthesis of multinuclear Rh(I) complexes bearing triazolylidenes and their application in C-C and c-Si bond forming reactions

Multidentate carbene ligands are valuable frameworks for the preparation of carbene complexes displaying higher nuclearity. In the present work, we report the synthesis of a series of mono- to tetra-[Rh(COD)I] complexes (3a- d) supported by mesoionic triazol-5-ylidenes. The general synthetic procedure involves the one step reaction of the appropriate triazolium (2a-d) salt in the presence of KHMDS and stoiquiometric amounts of the rhodium(I) precursor. Treatment of complexes 3a-d with an excess of carbon monoxide allows for the quantitative preparation of complexes 4a-d featuring a [Rh(CO)2I] fragment used for the detemination of the donor properties of the new triazolylidene ligands. All complexes have been fully characterized by means of 1H and 13C NMR spectroscopy, melting point, elemental analysis, and in the case of complex 3a, by X-ray crystallography. Comparison of the catalytic activity of the new rhodium complexes in C-C and C-Si bond forming processes demonstrate the enhanced performance of the tetranuclear species suggesting the possibility of strong cooperative effects in these multinuclear complexes.

Palladium-catalyzed olefination of aryl/alkyl halides with trimethylsilyldiazomethane via carbene migratory insertion

The direct olefination of aryl/alkyl halides with trimethylsilyldiazomethane (TMSD) as a C1- or C2-unit was achieved successfully via a metal carbene migratory insertion process, which offered a new access to afford (E)-vinyl silanes and (E)-silyl-substituted α,β-unsaturated amides in good yields and high chemoselectivity.

Stereoselective Transfer Semi-Hydrogenation of Alkynes to E-Olefins with N-Heterocyclic Silylene–Manganese Catalysts

The synthesis and structures of the first SiII-donor supported manganese(II) complexes [L1]MnCl2, [L2]MnCl2, and [L3]2MnCl2 are reported, bearing a pincer-type bis(NHSi)-pyridine ligand L1, bidentate bis(NHSi)-ferrocene ligand L2, and two monodentate NHSi ligands L3 (NHSi = N-heterocyclic silylene), respectively. They act as unprecedented very active and stereoselective Mn-based precatalysts (1 mol % loading) in transfer semi-hydrogenations of alkynes to give the corresponding E-olefins using ammonia–borane as a convenient hydrogen source under mild reaction conditions. Complex [L1]MnCl2 shows the best catalytic performance with quantitative conversion rates and excellent E-stereoselectivities (up to 98 %) for different alkyne substrates. Different types of functional groups can be tolerated, except CN, NH2, NO2, and OH groups at the phenyl group of 1-phenyl substituted alkynes.

Alkyne Semihydrogenation with a Well-Defined Nonclassical Co-H2 Catalyst: A H2 Spin on Isomerization and E-Selectivity

The reactivity of a CoI-H2 complex was extended toward the semihydrogenation of internal alkynes. Under ambient temperatures and moderate pressures of H2, a broad scope of alkynes were semihydrogenated using a CoI-N2 precatalyst, resulting in the formation of trans-alkene products. Furthermore, mechanistic studies using 1H, 2H, and para-hydrogen induced polarization (PHIP) transfer NMR spectroscopy revealed cis-hydrogenation of the alkyne occurs first. The Co-mediated alkene isomerization afforded the E-selective products from a broad group of alkynes with good yields and E/Z selectivity.

Synthesis of (E)-(2-Arylethenyl)silanes by Palladium-Catalyzed Arylation of Vinylsilanes in the Presence of Silver Nitrate

A series of (E)-trimethyl(2-arylethenyl)silanes 1-16 and (E)-triethoxy(2-arylethenyl)silanes 17 and 18 has been synthesized by palladium-catalyzed arylation of the corresponding vinylsilanes, in the presence of silver nitrate.Apart from enhancing the rate of the reaction, silver nitrate also completely suppresses the desilylation.In the absence of silver salt, under ordinary Heck arylation conditions, styrene derivatives are formed in good yields.A possible mechanistic rationale for the formation of styrenes is discussed.