26216-93-3

Usage

Synthesis Reference(s)

The Journal of Organic Chemistry, 46, p. 3575, 1981 DOI: 10.1021/jo00330a050

Upstream product

• 62058-93-9 1,1,2-trimethyl-indolinium; iodide 
• 6872-06-6 2-methyl indoline 
• 74-88-4 methyl iodide 
• 875-79-6 1,2-dimethylindole 
• 64-18-6 formic acid 
• 90563-52-3 α-methylindole 
• 95-20-5 2-methyl-1H-indole 
• 50-00-0 formaldehyd 
• 124-38-9 carbon dioxide 
• 274-07-7 benzo[1,3,2]dioxaborole 
• 67-68-5 dimethyl sulfoxide 
• 917377-80-1 2-methylindoline allyl carbamate 
• 7647-01-0 hydrogenchloride 
• 6628-07-5 N-allyl-N-methylaniline 

Downstream Products

• 887690-37-1 1,2-dimethyl-indoline-5-carbaldehyde 
• 62058-93-9 1,1,2-trimethyl-indolinium; iodide 
• 87401-40-9 1,2-dimethyl-octahydro-indole 
• 87926-14-5 2-propyl-N-methyl-aniline 
• 87401-40-9 (+/-)-1,2ξ-dimethyl-(3ar,7at)-octahydro-indole 
• 875-79-6 1,2-dimethylindole 

Relevant academic research and scientific papers

Utilization of renewable formic acid from lignocellulosic biomass for the selective hydrogenation and/or N-methylation

Lignocellulosic biomass is one of the most abundant renewable sources in nature. Herein, we have developed the utilization of renewable formic acid from lignocellulosic biomass as a hydrogen source and a carbon source for the selective hydrogenation and further N-methylation of various quinolines and the derivatives, various indoles under mild conditions in high efficiencies. N-methylation of various anilines is also developed. Mechanistic studies indicate that the hydrogenation occurs via a transfer hydrogenation pathway.

Dirhodium-Catalyzed Chemo-and Site-Selective C-H Amidation of N, N-Dialkylanilines

A method for dirhodium-catalyzed C(sp 3)-H amidation of N, N-dimethylanilines was developed. Chemoselective C(sp 3)-H amidation of N-methyl group proceeded exclusively in the presence of C(sp 2)-H bonds of the electron-rich aromatic ring. Site-selective C(sp 3)-H amidation proceeded exclusively at the N-methyl group of N-methyl-N-Alkylaniline derivatives with secondary, tertiary, and benzylic C(sp 3)-H bonds α to a nitrogen atom.

Selective C-H Olefination of Indolines (C5) and Tetrahydroquinolines (C6) by Pd/S,O-Ligand Catalysis

Herein, we report a highly selective C-H olefination of directing-group-free indolines (C5) and tetrahydroquinolines (C6) by Pd/S,O-ligand catalysis. In the presence of the S,O-ligand, a wide range of challenging indolines, tetrahydroquinolines, and olefins was efficiently olefinated under mild reaction conditions. The synthetic potential of this methodology was demonstrated by the efficient olefination of several indoline-based natural products.

Iron-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2

We herein describe an efficient iron-catalyzed selective N-methylation and N-formylation of amines with CO2 and silane using mono-phosphine as ligand. With commercially available [CpFe(CO)2]2 as catalyst, Fe-catalyzed methylation of amines was achieved with triphenylphosphine as a ligand. Using tributylphosphine as a ligand, Fe-catalyzed formylation of amines was realized at a lower temperature. The method was successfully applied in the late-stage methylation and formylation of drug molecules containing amine moiety. (Figure presented.).

B(C6F5)3-Catalyzed C3-Selective C-H Borylation of Indoles: Synthesis, Intermediates, and Reaction Mechanism

Without the addition of any additives and production of any small molecules, C3-borylated indoles and transfer hydrogenated indolines have been simultaneously achieved by a B(C6F5)3-catalyzed disproportionation reaction of a broad range of indoles with catecholborane. This catalyst system exhibits excellent catalytic performance for practical applications, such as easy scale-up under solvent-free conditions and long catalytic lifetime over ten sequential additions of starting materials. A combined mechanistic study, including isolation and characterization of key reaction intermediates, analysis of the disproportionation nature of the reaction, in situ NMR of the reaction, and analysis of detailed experimental data, has led to a possible reaction mechanism which illustrates pathways for the formation of both major products and byproducts. Understanding the reaction mechanism enables us to successfully suppress side reactions by choosing appropriate substrates and adjusting the amount of catecholborane needed. More importantly, with an elevated reaction temperature, we could achieve the convergent disproportionation reaction of indoles, in which indolines were continuously oxidized to indoles for the next disproportionation catalytic cycle. Near quantitative conversions and up to 98% yields of various C3-selective borylated indoles were achieved, without any additives or H2 acceptors.

Diverse catalytic reactivity of a dearomatized PN3P?-nickel hydride pincer complex towards CO2 reduction

A dearomatized PN3P?-nickel hydride complex has been prepared using an oxidative addition process. The first nickel-catalyzed hydrosilylation of CO2 to methanol has been achieved, with unprecedented turnover numbers. Selective methylation and formylation of amines with CO2 were demonstrated by such a PN3P?-nickel hydride complex, highlighting its versatile functions in CO2 reduction.

DBU-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2 and Polymethylhydrosiloxane

We describe herein an efficient organocatalytic system for the selective N-methylation and N-formylation of amines with carbon dioxide (CO2) as a sustainable C1 feedstock and polymethylhydrosiloxane (PMHS) as a cost-effectvie reducing reagent. High-yielding N-methylation products are obtained with low catalyst loading (1%) of DBU. Selective N-formylation of amines is achieved using the same catalytic system at a lower reaction temperature. (Figure presented.).

METHOD FOR HYDROGENATING UNSATURATED COMPOUND

PROBLEM TO BE SOLVED: To provide a method for hydrogenating an unsaturated compound that uses crude gaseous hydrogen having carbon monoxide and carbon dioxide coexist with each other, as a hydrogen source. SOLUTION: A method for hydrogenating an unsaturated compound uses crude gaseous hydrogen as a hydrogen source and is performed in the presence of a frustrated Lewis pair. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT

Methylation of aromatic amines and imines using formic acid over a heterogeneous Pt/C catalyst

We describe here a commercially available Pt/C catalyst capable of catalyzing the methylation of anilines and aromatic imines with formic acid in the presence of a hydrosilane reductant. Both primary aniline and secondary aniline can be methylated. The advantage of this newly described method includes operational simplicity, high TON, ready availability of the catalyst, and also good functional group compatibility.

Frustrated Lewis Pair Catalyzed Dehydrogenative Oxidation of Indolines and Other Heterocycles

An acceptorless dehydrogenation of heterocycles catalyzed by frustrated Lewis pairs (FLPs) was developed. Oxidation with concomitant liberation of molecular hydrogen proceeded in high to excellent yields for N-protected indolines as well as four other substrate classes. The mechanism of this unprecedented FLP-catalyzed reaction was investigated by mechanistic studies, characterization of reaction intermediates by NMR spectroscopy and X-ray crystal analysis, and by quantum-mechanical calculations. Hydrogen liberation from the ammonium hydridoborate intermediate is the rate-determining step of the oxidation. The addition of a weaker Lewis acid as a hydride shuttle increased the reaction rate by a factor of 2.28 through a second catalytic cycle.