132994-41-3

Upstream product

• 98-86-2 acetophenone 
• 98-88-4 benzoyl chloride 
• 19269-14-8 sodium dibenzoylmethane 
• 1704-15-0 3-hydroxy-1,3-diphenyl-2-propen-1-one 
• 1458-98-6 2-methyl-3-bromo-1-propene 
• 120-46-7 1,3-diphenylpropanedione 
• 18292-38-1 2-methallyltrimethylsilane 

Downstream Products

• 1179891-06-5 1-(4-methoxyphenyl)-4-(2-methylallyl)-3,5-diphenyl-1H-pyrazole 
• 1179891-04-3 1-methyl-4-(2-methylallyl)-3,5-diphenyl-1H-pyrazole 
• 1609650-64-7 C₂₂H₂₀O₂ 
• 1609650-43-2 2-(2-methylallyl)-1,3-diphenyl-2-(3-phenylprop-2-ynyl)propane-1,3-dione 

Relevant academic research and scientific papers

Nucleophilic Addition to π-Allyl Gold(III) Complexes: Evidence for Direct and Undirect Paths

π-Allyl complexes play a prominent role in organometallic chemistry and have attracted considerable attention, in particular the π-allyl Pd(II) complexes which are key intermediates in the Tsuji-Trost allylic substitution reaction. Despite the huge interest in π-complexes of gold, π-allyl Au(III) complexes were only authenticated very recently. Herein, we report the reactivity of (P,C)-cyclometalated Au(III) π-allyl complexes toward β-diketo enolates. Behind an apparently trivial outcome, i.e. the formation of the corresponding allylation products, meticulous NMR studies combined with DFT calculations revealed a complex and rich mechanistic picture. Nucleophilic attack can occur at the central and terminal positions of the π-allyl as well as the metal itself. All paths are observed and are actually competitive, whereas addition to the terminal positions largely prevails for Pd(II). Auracyclobutanes and π-alkene Au(I) complexes were authenticated spectroscopically and crystallographically, and Au(III) σ-allyl complexes were unambiguously characterized by multinuclear NMR spectroscopy. Nucleophilic additions to the central position of the π-allyl and to gold are reversible. Over time, the auracyclobutanes and the Au(III) σ-allyl complexes evolve into the π-alkene Au(I) complexes and release the C-allylation products. The relevance of auracyclobutanes in gold-mediated cyclopropanation was demonstrated by inducing C-C coupling with iodine. The molecular orbitals of the π-allyl Au(III) complexes were analyzed in-depth, and the reaction profiles for the addition of β-diketo enolates were thoroughly studied by DFT. Special attention was devoted to the regioselectivity of the nucleophilic attack, but C-C coupling to give the allylation products was also considered to give a complete picture of the reaction progress.

Copper-Catalyzed Modular Amino Oxygenation of Alkenes: Access to Diverse 1,2-Amino Oxygen-Containing Skeletons

Copper-catalyzed alkene amino oxygenation reactions using O-acylhydroxylamines have been achieved for a rapid and modular access to diverse 1,2-amino oxygen-containing molecules. This transformation is applicable to the use of alcohols, carbonyls, oximes, and thio-carboxylic acids as nucleophiles on both terminal and internal alkenes. Mild reaction conditions tolerate a wide range of functional groups, including ether, ester, amide, carbamate, and halide. The reaction protocol allows for starting with free amines as the precursor of O-benzoylhydroxylamines to eliminate their isolation and purification, contributing to broader synthetic utilities. Mechanistic investigations reveal the amino oxygenation reactions may involve distinct pathways, depending on different oxygen nucleophiles.

Electrochemical oxidative cyclization of olefinic carbonyls with diselenides

The tandem cyclization of olefinic carbonyls with easily accessible diselenides facilitated by electrochemical oxidation has been successfully developed, which provides an environmentally friendly method for the construction of C-Se and C-O bonds simultaneously. A series of seleno dihydrofurans and seleno oxazolines, bearing fragile heterocycles, subtle C-I bonds and supernumerary vinyl groups, were forged using this elegant chelation strategy. Neither metal catalysts nor external chemical oxidants are required to promote this transformation.

Organic base-catalysed solvent-tuned chemoselective carbotrifluoromethylation and oxytrifluoromethylation of unactivated alkenes

An unprecedented and efficient organic base-catalysed highly chemoselective carbo- and oxytrifluoromethylation of unactivated alkenes with Togni's reagent was developed. The switchable chemoselectivity was tuned by simply changing the organic base catalyst and solvent. Mechanistic studies indicated that a radical cyclization pathway for carbotrifluoromethylation in DMSO and a carbocation pathway for oxytrifluoromethylation in DCE were probably involved.

Enantioselective cycloisomerization of 1,6-enynes to bicyclo[3.1.0]hexanes catalyzed by rhodium and benzoic acid

It has been established that a cationic Rh(I)/(S)-Segphos or (S)-DTBM-Segphos complex and benzoic acid catalyze the enantioselective cycloisomerization of 1,6-enynes, possessing carbonyl groups at the enyne linkage, to 2-alkylidenebicyclo[3.1.0]hexanes. The present cycloisomerization may involve site selective γ-hydrogen elimination. The one-pot enantioselective cycloisomerization and lactonization of 1,6-enynes, leading to bicyclic lactones, has also been accomplished.

Catalytic, enantioselective, and highly chemoselective bromocyclization of olefinic dicarbonyl compounds

Overriding preferences: An amine-thiocarbamate catalyst can mediate the facile, efficient, and highly enantioselective bromocyclization of olefinic 1,3-dicarbonyl compounds. In the presence of the bifunctional catalyst, the bromination occurs chemoselectively at the olefinic moiety rather than at the carbon atom in the α-position to the carbonyl units. Copyright

Facile route to tetrasubstituted pyrazoles utilizing ceric ammonium nitrate

A convenient approach for the synthesis of tetrasubstituted pyrazoles is described. The method involves the treatment of 1,3-diketones and allyltrimethylsilane with CAN followed by ceriumcatalyzed addition of substituted hydrazines to construct pyrazoles in good yields. Georg Thieme Verlag Stuttgart.