5336-72-1

Upstream product

• 64-18-6 formic acid 
• 20599-29-5 (α-butoxy-benzyl)-dimethyl-amine 
• 71964-91-5 benzhydryl-trimethyl-ammonium; bromide 
• 151-50-8 potassium cyanide 
• 107-21-1 ethylene glycol 
• 124-40-3 dimethyl amine 
• 90-99-3 diphenylchloromethane 
• 776-74-9 Bromodiphenylmethane 
• 68-12-2 N,N-dimethyl-formamide 
• 91-01-0 1,1-Diphenylmethanol 
• 3768-60-3 N,N,N',N'-tetramethylsulfurous acid diamine 
• 62999-86-4 5,5-Dimethyl-2-N,N-dimethylamino-1,3-dioxane 
• 5780-17-6 (bis-ethylsulfanyl-methyl)-dimethyl-amine 
• 50-00-0 formaldehyd 

Downstream Products

• 32245-28-6 benzhydryl-trimethyl-ammonium; hydroxide 
• 132751-41-8 2-dimethylamino-1,3,3-triphenyl-propan-1-one 
• 7495-83-2 n-butyl diphenylmethyl ether 
• 79841-49-9 benzhydryl(dimethyl)-(3-phenylprop-2-ynyl)ammonium bromide 
• 117-34-0 2,2-diphenylacetic acid 
• 113569-93-0 O-benzhydryl-N,N-dimethyl-hydroxylamine 
• 101-81-5 Diphenylmethane 
• 119-61-9 benzophenone 
• 62861-50-1 benzophenone-¹⁸O 
• 79841-50-2 3-dimethylamino-1,4,4-triphenylbut-1-yne 
• 113090-88-3 benzhydryl-dimethyl-amine oxide 

Relevant academic research and scientific papers

Simplified preparation of a graphene-co-shelled Ni/NiO@C nano-catalyst and its application in theN-dimethylation synthesis of amines under mild conditions

The development of Earth-abundant, reusable and non-toxic heterogeneous catalysts to be applied in the pharmaceutical industry for bio-active relevant compound synthesis remains an important goal of general chemical research.N-methylated compounds, as one of the most essential bioactive compounds, have been widely used in the fine and bulk chemical industries for the production of high-value chemicals. Herein, an environmentally friendly and simplified method for the preparation of graphene encapsulated Ni/NiO nanoalloy catalysts (Ni/NiO@C) was developed for the first time, for the highly selective synthesis ofN-methylated compounds using various functional amines and aldehydes under easy to handle, and industrially applicable conditions. A large number of primary and secondary amines (more than 70 examples) could be converted to the correspondingN,N-dimethylamines with the participation of different functional aldehydes, with an average yield of over 95%. A gram-scale synthesis also demonstrated a similar yield when compared with the benchmark test. In addition, it was further proved that the catalyst could easily be recycled because of its intrinsic magnetism and reused up to 10 times without losing its activity and selectivity. Also, for the first time, the tandem synthesis ofN,N-dimethylamine products in a one-pot process, using only a single earth-abundant metal catalyst, whose activity and selectivity were more than 99% and 94%, respectively, for all tested substrates, was developed. Overall, the advantages of this newly developed method include operational simplicity, high stability, easy recyclability, cost-effectiveness of the catalyst, and good functional group compatibility for the synthesis ofN-methylation products as well as the industrially applicable tandem synthesis process.

Synthesis of: N -methylated amines from acyl azides using methanol

The transformation of acyl azide derivatives into N-methylamines was developed using methanol as the C1 source via the one-pot Curtius rearrangement and borrowing hydrogen methodology. Following this protocol, various functionalised N-methylated amines were synthesized using the (NNN)Ru(ii) complex from carboxylic acids via an acyl azide intermediate. Several kinetic studies and DFT calculations were carried out to support the mechanism and also to determine the role of the Ru(ii) complex and base in this transformation.

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.

Iridium-Catalyzed Reductive Strecker Reaction for Late-Stage Amide and Lactam Cyanation

A new iridium-catalyzed reductive Strecker reaction for the direct and efficient formation of α-amino nitrile products from a broad range of (hetero)aromatic and aliphatic tertiary amides, and N-alkyl lactams is reported. The protocol exploits the mild and highly chemoselective reduction of the amide and lactam functionalities using IrCl(CO)[P(C6H5)3]2 (Vaska's complex) in the presence of tetramethyldisiloxane, as a reductant, to directly generate hemiaminal species able to undergo substitution by cyanide upon treatment with TMSCN (TMS=trimethylsilyl). The protocol is simple to perform, broad in scope, efficient (up to 99 % yield), and has been successfully applied to the late-stage functionalization of amide- and lactam-containing drugs, and naturally occurring alkaloids, as well as for the selective cyanation of the carbonyl carbon atom linked to the N atom of proline residues within di- and tripeptides.

Methyl fluoroalkanoate as methyl-transferring reagent. Unexpected participation of BAl2 (SN2) mechanism in the reaction of methyl 2,3,3,3-tetrafluoro-2-methoxypropanoate with amines

In the reaction of methyl 2,3,3,3-tetrafluoro-2-methoxypropanoate with arylamines or arylmethylamines, an unexpected methyl transfer from the ester to the amine by the BAl2 (SN2) mechanism was observed leading to the corresponding N-methylamines under specific conditions. The reaction was accompanied by the formation of amides via BAc2 mechanism. The unexpected methyl transfer is highly dependent on the structure of the starting amine and is supported by the absence of solvent and high temperature.

Methanol dehydrogenation by iridium N-heterocyclic carbene complexes

A series of homogeneous iridium bis(N-heterocyclic carbene) catalysts are active for three transformations involving dehydrogenative methanol activation: acceptorless dehydrogenation, transfer hydrogenation, and amine monoalkylation. The acceptorless dehydrogenation reaction requires base, yielding formate and carbonate, as well as 2-3 equivalents of H2. Of the few homogeneous systems known for this reaction, our catalysts tolerate air and employ simple ligands. Transfer hydrogenation of ketones and imines from methanol is also possible. Finally, N-monomethylation of anilines occurs through a borrowing hydrogen reaction. Notably, this reaction is highly selective for the monomethylated product.

General one-pot reductive gem-bis-alkylation of tertiary lactams/amides: Rapid construction of 1-azaspirocycles and formal total synthesis of (±)-cephalotaxine

Amides are a class of highly stable and readily available compounds. The amide functional group constitutes a class of powerful directing/activating and protecting group for C-C bond formation. Tertiary tert-alkylamine, including 1-azaspirocycle is a key structural feature found in many bioactive natural products and pharmaceuticals. The transformation of amides into tert-alkylamines generally requires several steps. In this paper, we report the full details of the first general method for the direct transformation of tertiary lactams/amides into tert-alkylamines. The method is based on in situ activation of amide with triflic anhydride/2,6-di-tert-butyl-4-methylpyridine (DTBMP), followed by successive addition of two organometallic reagents of the same or different kinds to form two C-C bonds. Both alkyl and functionalized organometallic reagents and enolates can be used as the nucleophiles. The method displayed excellent 1,2- and good 1,3-asymmetric induction. Construction of 1-azaspirocycles from lactams required only two steps or even one-step by direct spiroannelation of lactams. The power of the method was demonstrated by a concise formal total synthesis of racemic cephalotaxine. Four bonds in one pot! Cleavage of two bonds of an amide carbonyl group and replacement by two new C-C bonds can be achieved in one pot under mild conditions by using amide activation with triflic anhydride (Tf2O). A concise formal total synthesis of racemic cephalotaxine has been accomplished by means of this methodology (see scheme; DTBMP=2,6-di-tert-butyl-4-methylpyridine). Copyright

Sequential one-pot reactions of thioformamides with organolithium and zinc reagents

Sequential one-pot reactions of thioformamides with organolithium and zinc reagents were carried out. As thioformamides, N,N-dimethylthioformamide and N-ethoxycarbonyl N′-thioformyl piperazine were used. A variety of organolithium reagents such as alkyl, aryl, and heteroaryllithiums were used to give the corresponding amines in moderate to high yields. The efficiency of the reaction was influenced by the substituents on the aromatic rings. Thienyllithium gave the product in good yield, whereas the reaction offuryllithium was less efficient. A similar reaction with lithium acetylides was not successful. As an alternative method, methyl iodide was added to the reaction mixture ofthioformamides and lithium silylacetylide to form S,N-acetals as intermediates, and to this were added organozinc reagents to lead to propargylamines. For organozinc reagents, dialkyl zincs and 3- ethoxycarbonylpropylzinc bromide were used. The former reagents showed high efficiency when combined with several organolithium reagents, but the latter gave the corresponding product only when lithium silylacetylide was used as an initial reagent. Copyright Taylor & Francis Group, LLC.

Direct, one-pot sequential reductive alkylation of lactams/amides with grignard and Organolithium reagents through lactam/amide activation

(Figure Presented) Be dazzled by the sequence: The first efficient and general one-pot method for the reductive bisalkylation of lactams/ amides with Grignard and organolithium reagents has been developed (see scheme; DTBMP = 2,6-di-tert-butyl-4methylpyridine, Tf=trifluoromethanesulfonyl).

Synthesis of tertiary sec-alkylamines by the addition of grignard reagents to N,N-dialkylformamides mediated by Ti(OiPr)4 and Me3SiCl

A number of tertiary sec-alkylamines (22 examples, 29-80% yield) have been prepared according to a simple one-pot procedure by the addition of Grignard reagents to N,N-dialkylformamides in the presence of Ti(OiPr)4 and Me3SiCl. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.