34143-89-0

Upstream product

• 100-42-5 styrene 
• 88-05-1 2,4,6-trimethylaniline 
• 14213-00-4 2,4,6-trimethylaniline azide 
• 6554-98-9 trans-4-Hydroxystilbene 
• 100-52-7 benzaldehyde 
• 100-51-6 benzyl alcohol 
• 100-46-9 benzylamine 
• 594-19-4 tert.-butyl lithium 
• 6630-33-7 ortho-bromobenzaldehyde 
• 124862-47-1 azidotri-2,4,6-trimethylphenylgermane 
• 83686-80-0 dimesitylchlorogermane 

Downstream Products

• 1044499-42-4 (S)-2-cyclohexyl-2,3-dihydroquinazolin-4(1H)-one 
• 1044499-41-3 (R)-2-phenyl-2,3-dihydroquinazolin-4(1H)-one 
• 60882-91-9 N-(2-fluorobenzyl)-1-2,4,6-trimethyl-aniline 
• 85975-68-4 N-(Ethoxycarbonyl)-3-mesityl-4-phenyl-1,3-thiazetidin-2-imin 

Relevant academic research and scientific papers

[(PPh3)2NiCl2]-Catalyzed C-N bond formation reaction via borrowing hydrogen strategy: Access to diverse secondary amines and quinolines

Commercially available [(PPh3)2NiCl2] was found to be an efficient catalyst for the mono-N-alkylation of (hetero)- A romatic amines, employing alcohols to deliver diverse secondary amines, including the drug intermediates chloropyramine (5b) and mepyramine (5c), in excellent yields (up to 97%) via the borrowing hydrogen strategy. This method shows a superior activity (TON up to 10000) with a broad substrate scope at a low catalyst loading of 1 mol % and a short reaction time. Further, this strategy is also successful in accessing various quinoline derivatives following the acceptorless dehydrogenation pathway.

Iron-Catalyzed Nitrene Transfer Reaction of 4-Hydroxystilbenes with Aryl Azides: Synthesis of Imines via C=C Bond Cleavage

C=C bond breaking to access the C=N bond remains an underdeveloped area. A new protocol for C=C bond cleavage of alkenes under nonoxidative conditions to produce imines via an iron-catalyzed nitrene transfer reaction of 4-hydroxystilbenes with aryl azides is reported. The success of various sequential one-pot reactions reveals that the good compatibility of this method makes it very attractive for synthetic applications. On the basis of experimental observations, a plausible reaction mechanism is also proposed.

Unprecedented Copper(II) Complex with a Topoquinone-like Moiety as a Structural and Functional Mimic for Copper Amine Oxidase: Role of Copper(II) in the Genesis and Amine Oxidase Activity

Copper amine oxidase (CAO), consisting of the topoquinone (TPQ) cofactor, catalyzes the oxidation of primary amines to aldehyde. We have successfully addressed this issue through isolation of a copper complex which mimics the active-site structure as well as the function of CAO. This inimitable complex, consisting of two TPQ-like side-arms, formed by ambient aerial oxidation of a precursor Schiff base complex, is the most efficient homogeneous catalyst for quantitative oxidation of primary benzylic amines to corresponding secondary imines under ambient conditions within 30 min. The longstanding contention of actual involvement of Cu(II) in the catalysis is resolved through quenching experiments of Cu(II) superoxo species and detailed density functional theory studies.

Lithium–Bromide Exchange versus Nucleophilic Addition of Schiff's base: Unprecedented Tandem Cyclisation Pathways

By exploring lithium–bromide exchange reactivity of aromatic Schiff's bases with tert-butyllithium (tBuLi), we have revealed unprecedented competitive intermolecular and intramolecular cascade annulation pathways, leading to valuable compounds, such as iso-indolinones and N-substituted anthracene derivatives. A series of reaction parameters were probed, including solvent, stoichiometry, sterics and organolithium reagent choice, in order to understand the influences that limit such ring-closing pathways. With two viable reactivity options for the organolithium on the imine; namely, nucleophilic addition or lithium–bromide exchange, a surprising competitive nature was observed, where nucleophilic addition dominated, even under cryogenic conditions. Considering the most commonly used solvents for lithium–bromide exchange, tetrahydrofuran (THF) and diethyl ether (Et2O), contrasting reactivity outcomes were revealed with nucleophilic addition promoted in THF, while Et2O yielded almost double the conversion of cyclic products than in THF.

Readily Available Primary Aminoboranes as Powerful Reagents for Aldimine Synthesis

Primary aminoboranes (RNHBR2), which are readily available by spontaneous dehydrocoupling of amines and boranes cleanly react at room temperature with aldehydes to give aldimines. The overall transformation from amines to aldimines can be conveniently performed by a sequential one-pot reaction. This synthetic strategy is especially useful for electron poor and bulky amines which are reluctant to react with aldehydes under dehydration conditions. Using a Glorius robustness screen, we show that this methodology is chemoselective, and functional group tolerant. Computational and experimental data support the irreversible formation of the aldimine product in marked contrast with traditional methods.

Tris(2,4,6-trifluorophenyl)borane: An Efficient Hydroboration Catalyst

The metal-free catalyst tris(2,4,6-trifluorophenyl)borane has demonstrated its extensive applications in the 1,2-hydroboration of numerous unsaturated reagents, namely alkynes, aldehydes and imines, consisting of a wide array of electron-withdrawing and donating functionalities. A range of over 50 borylated products are reported, with many reactions proceeding with low catalyst loading under ambient conditions. These pinacol boronate esters, in the case of aldehydes and imines, can be readily hydrolyzed to leave the respective alcohol and amine, whereas alkynyl substrates result in vinyl boranes. This is of great synthetic use to the organic chemist.

Mn-catalyzed three-component reactions of imines/nitriles, grignard reagents, and tetrahydrofuran: An expedient access to 1,5-amino/keto alcohols

An expedient Mn-catalyzed three-component synthesis of 1,5-amino/keto alcohols from Grignard reagents, imines/nitriles, and tetrahydrofuran (THF) is described, which deviates from the classic Grignard addition to imines/nitriles in THF solvent. THF is split and sewn in an unprecedented manner in the reaction, leading to the formation of two geminal C-C bonds via C-H and C-O cleavage. Mechanistic experiments and DFT calculations reveal radical and organo-Mn intermediates in the catalytic cycle and the α-arylative ring-opening of THF as the key reaction step.

Catalytic asymmetric synthesis of dihydroquinazolinones from imines and 2-aminobenzamides

An unprecedented catalytic asymmetric synthesis of aminal-containing heterocyclic compounds has been developed from imines and tethered nitrogen/nitrogen nucleophiles. In the presence of 10mol% of a commercially available chiral phosphoric acid, a range of aromatic, α,β- unsaturated, and aliphatic imines react with 2-aminobenzamides to give dihydroquinazolinones in good to excellent yields and ee. The enantioselectivity is significantly affected by the imine N-substituent through non-bonding interactions with the chiral phosphoric acid and the 2-aminobenzamide. Copyright

Catalytic intermolecular hetero-dehydro-diels-alder cycloadditions: Regioand diasteroselective synthesis of 5,6-dihydropyridin-2-ones

A novel catalyzed intermolecular heterodehydro-Diels-Alder reaction between push-pull 1,3-dien-5-ynes and aldimines or silylaldimines is reported. The sequence is promoted both by gold(I) or silver(I) catalysts and leads to the diastereo- and regioselective formation of 5,6- dihydropyridin-2-ones.

N-Mesityl dimesitylgerma-imine

N-Mesityldimesitylgermaimine (1) which is obtained by photolysis of trimesitylgermylazide has also been detected in the reaction of dimesitylgermylene with mesitylazide. 1 was characterized at room temperature by its pseudo-Wittig reaction with benzaldehy