94397-80-5

Upstream product

• 459-44-9 4-methylbenzenediazonium tetrafluoroborate 
• 754-05-2 ethenyltrimethylsilane 
• 617-86-7 triethylsilane 
• 766-97-2 4-n-methylphenylacetylene 
• 122-00-9 para-methylacetophenone 
• 615-65-6 2-chloro-4-methyl-benzenamine 
• 49750-22-3 1-(trimethylsilyl)vinylmagnesium bromide 
• 116632-42-9 2-chloro-1-iodo-4-methylbenzene 
• 938-81-8 N-nitrosoacetanilide 
• 10557-67-2 N-nitroso-p-methyl-acetanilide 
• 195062-57-8 p-tolylboronic pinacol ester 

Downstream Products

• 100-70-9 2-Cyanopyridine 
• 100-48-1 pyridine-4-carbonitrile 
• 100-54-9 pyridine-3-carbonitrile 

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.

Catalyst-Free Enantiospecific Olefination with In Situ Generated Organocerium Species

Described is the in situ formation of triorganocerium reagents and their application in catalyst-free Zweifel olefinations. These unique cerium species were generated through novel exchange reactions of organohalides with n-Bu3Ce reagents. The adequate electronegativity of cerium allowed for compensating the disadvantages of both usually functional-group-sensitive organolithium species and less reactive organomagnesium reagents. Exchange reactions were performed on aryl and alkenyl bromides, enabling enantiospecific transformations of chiral boron pinacol esters. Finally, these new organocerium species were engaged in selective 1,2-additions onto enolisable and sterically hindered ketones.

Preparation of Optically Active cis-Cyclopropane Carboxylates: Cyclopropanation of α-Silyl Stryenes with Aryldiazoacetates and Desilylation of the Resulting Silyl Cyclopropanes

Optically active cis-cyclopropane carboxylates are prepared via the Rh2(S-PTAD)4-catalyzed cyclopropanation of α-silyl styrenes with aryl diazoacetates followed by desilylation of the resulting silyl cyclopropane carboxylates. The co

VINYLSILYL GRIGNARD REAGENTS AS ARYNE TRAPS. A NEW ROUTE TO (ARYLALKENYL)SILANES.

A general method for preparing (arylalkenyl)silanes via nucleophilic capture of arynes with vinyltrimethylsilyl Grignard reagents is decribed.

Stereospecific Arylation of Alkenylsilanes with Arylpalladium Acetates

Alkenyltrimethylsilanes ((E)- and (Z)-RCH=CHSiMe3: R = H, Ph, n-C6H13 and CH3OCH2) stereospecifically reacted at 40 deg C or room temperature with in situ generated phenylpalladium acetate to produce R(Ph)C=CSiMe3 and RCH=C(Ph)SiMe3 with inversion of their geometry.The arylation of CH2=CHSiMe3 with arylpalladium acetates gave (E)-ArCH=CHSiMe3 (Ar = XPH; X = H, 4-Me, 4-MeO, 4-Br, 4-I, 4-EtOCO, and 4-NO2) in good yields.

REACTION OF DIAZONIUM SALTS WITH TRANSITION METALS IX. REACTION OF VINYLTRIMETHYLSILANE WITH ARENEDIAZONIUM TETRAFLUOROBORATES UNDER PALLADIUM(0) CATALYSIS

Arenediazonium tetrafluoroborates (ArN2BF4 where Ar = Ph, 4-MeC6H4, 4-BrC6H4, 4-IC6H4 and 4-NO2C6H4) reacted easily with CH2=CHSiMe3 at 25 deg C to give ArCH=CH2, (E)-ArCH=CHSiMe3 and Ar(Me3Si)C=CH2 in excellent yields under palladium(0) catalysis. (E)-ArCH=CHSiMe3 compounds were obtained predominantly and isolated in good yields by using an excess of CH2=CHSiMe3 over ArN2BF4.Protodesilylation of the reaction mixture afforded styrene derivatives.