92249-42-8Relevant academic research and scientific papers
Indium-catalyzed reduction of secondary amides with a hydrosiloxane leading to secondary amines
Sakai, Norio,Takeoka, Masashi,Kumaki, Takayuki,Asano, Hirotaka,Konakahara, Takeo,Ogiwara, Yohei
supporting information, p. 6448 - 6451 (2015/11/16)
Described herein is that the selective reduction of aromatic/aliphatic secondary amides using a combination of InI3 and TMDS (1,1,3,3-tetramethyldisiloxane), which led to the production of the corresponding secondary amines. This reducing system showed a relatively high tolerance to a variety of functional groups, such as an alkyl, an alkoxy, a halogen, a cyano, an ether, a thioether, a heterocyclic ring, and a terminal alkene group.
Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids
Fu, Ming-Chen,Shang, Rui,Cheng, Wan-Min,Fu, Yao
, p. 9042 - 9046 (2015/08/03)
A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts.
Mechanism of the oxidation of aromatic sulfides catalysed by a water soluble iron porphyrin
Baciocchi, Enrico,Gerini, Maria Francesca,Lanzalunga, Osvaldo,Lapi, Andrea,Lo Piparo, Maria Grazia
, p. 422 - 426 (2007/10/03)
The oxygen atom transfer-electron transfer (ET) mechanistic dichotomy has been investigated in the oxidation of a number of aryl sulfides by H2O2 in acidic (pH 3) aqueous medium catalysed by the water soluble iron(III) porphyrin 5,10,15,20-tetraphenyl-21H,23H-porphine-p,p′,p″,p?-tetrasulfo nic acid iron(III) chloride (FeTPPSCl). Under these reaction conditions, the iron-oxo complex porphyrin radical cation, P+ Fe(IV)=O, should be the active oxidant. When the oxidation of a series of para-X substituted phenyl alkyl sulfides (X = OCH3, CH3, H, Br, CN) was studied the corresponding sulfoxides were the only observed product and the reaction yields as well as the reactivity were little influenced by the nature of X as well as by the bulkiness of the alkyl group. Labelling experiments using H2 18O or H218O2 clearly indicated that the oxygen atom in the sulfoxides comes exclusively from the oxidant. Moreover, no fragmentation products were observed in the oxidation of a benzyl phenyl sulfide whose radical cation is expected to undergo cleavage of the β C-H and C-S bonds. These results would seem to suggest a direct oxygen atom transfer from the iron-oxo complex to the sulfide. However, competitive experiments between thioanisole (E° = 1.49 V vs. NHE in H2O) and N,N-dimethylaniline (E° = 0.97 V vs. NHE in H2O) resulted in exclusive N-demethylation, whereas the oxidation of N-methylphenothiazine (10, E° = 0.95 V vs. NHE in CH3CN) and N,N-dimethyl-4-methylthioaniline (11, E° = 0.65 V vs. NHE in H2O) produced the corresponding sulfoxide with complete oxygen incorporation from the oxidant. Since an ET mechanism must certainly hold in the reactions of 10 and 11, the oxygen incorporation experiments indicate that the intermediate radical cation, once formed, has to react with PFe(IV)=O (the reduced form of the iron-oxo complex which is formed by the ET step) in a fast oxygen rebound. Thus, an ET step followed by a fast oxygen rebound is also suggested for the other sulfides investigated in this work.
Functionalized organolithium compounds of DTBB-catalyzed sulfur-lithium exchange
Foubelo, Francisco,Gutiérrez, Ana,Yus, Miguel
, p. 503 - 514 (2007/10/03)
The successive reaction of β- or γ-hydroxy or amino phenyl thioethers (1,4) with butyllithium and an excess of lithium powder in the presence of a catalytic amount of DTBB in THF at - 78°C leads to the formation of the corresponding β- or γ-functionalized organolithium compounds 2 or 5, respectively, which by treatment with different electrophiles [D2O, t- BuCHO, PhCHO, Me2CO, (CH2)4CO, (CH2)5CO] at temperatures ranging between - 78°C and room temperature yields, after hydrolysis with water, the expected functionalized alcohols or amines 3 or 6, respectively, in a completely regioselective manner.
The Use of 2-Oxazolidinones as Latent Aziridine Equivalents. 2. Aminoethylation of Aromatic Amines, Phenols, and Thiophenols
Poindexter, Graham S.,Owens, Donald A.,Dolan, Peter L.,Woo, Edmund
, p. 6257 - 6265 (2007/10/02)
The utility of 2-oxazolidinones 1 as latent, carboxylated aziridine functionalities was examined.Reaction of 2-oxazolidinone (1a), 3-methyl2-oxazolidinone (1b), 3-(phenylmethyl)-2-oxazolidinone (1c), 3-phenyl-2-oxazolidinone (1d) 4,4-dimethyl-2-oxazolidinone (1e), and 5-ethyl-2-oxazolidinone (1f) with aromatic amine salts, phenol, or thiophenols at elevated temperatures (> 130 deg C) afforded aminoethylated adducts.The aminoethylation occurred with concomitant loss of carbon dioxide to furnish variously substituted N-aryl-1,2-ethanediamines 4, 1-(2-phenoxyethyl)-2-imidazolidinone (8), or 2-(arylthio)ethanamines 9 on reactions of 1 with aromatic amine salts, phenol, and thiophenols, respectively.Imidazolidinone 8 is believed to be a secondary reaction product resulting from the condensation of the initially formed 2-phenoxyethanamine with starting oxazolidinone 1a.The aminoethylation reaction did not proceed with aliphatic amine hydrochlorides or alkyl mercaptans.Preliminary mechanistic pathways for these ring openings were also investigated employing a specific, C-5 deuterium-labeled oxazolidinone 1b-d2.Ring-opening experiments of 1b-d2 with N-methylaniline hydrochloride suggest reaction can occur through either a dioxazolinium 5 and/or 5 intermediate.In contrast, reaction of 1b-d2 with thiophenol suggests ring-opening to proceed only via the dioxazolinium pathway.
