183383-30-4

Usage

Uses

Used in Pharmaceutical Industry:
1-PIPERAZINECARBOXYLIC ACID,4-FORMYL-,1,1-DIMETHYLETHYL ESTER is used as a versatile intermediate for the synthesis of various pharmaceuticals due to its ability to be incorporated into the molecular structures of different medicinal compounds. Its role in drug development is crucial for creating new therapeutic agents with improved efficacy and safety profiles.
Used in Organic Chemistry:
In the field of organic chemistry, 1-PIPERAZINECARBOXYLIC ACID,4-FORMYL-,1,1-DIMETHYLETHYL ESTER is used as a building block for the synthesis of new organic compounds. Its unique structure allows for the creation of a variety of chemical entities that can be explored for their potential applications in various industries, including materials science, agrochemicals, and specialty chemicals.
While the provided materials do not specify particular applications beyond the synthesis of pharmaceuticals and other organic compounds, the compound's role as an intermediate suggests its utility in a broad range of chemical reactions and processes within the industries mentioned.

Upstream product

• 123855-51-6 tert-butyl 4-(hydroxymethyl)piperidin-1-carboxylate 
• 124-38-9 carbon dioxide 
• 57260-71-6 1-t-Butoxycarbonylpiperazine 
• 158328-38-2 1,2-N,N'-bisethane 
• 34619-03-9 tert-butyldicarbonate 
• 7755-92-2 piperazine-1-carbaldehyde 
• 1426682-55-4 t-butyl 4-pyridyl carbonate 
• 67-66-3 chloroform 
• 24424-99-5 di-tert-butyl dicarbonate 

Downstream Products

• 454217-55-1 1-[(4-chlorophenyl)phenylmethyl]-4-(tert-butoxycarbonyl)-piperazine 
• 53788-49-1 tert-butyl 4-methylpiperazine-1-carboxylate 

Relevant academic research and scientific papers

Catalyst freeN-formylation of aromatic and aliphatic amines exploiting reductive formylation of CO2using NaBH4

Herein, we report a sustainable approach forN-formylation of aromatic as well as aliphatic amines using sodium borohydride and carbon dioxide gas. The developed approach is catalyst free, and does not need pressure or a specialized reaction assembly. The reductive formylation of CO2with sodium borohydride generates formoxy borohydride speciesin situ, as confirmed by1H and11B NMR spectroscopy. Thein situformation of formoxy borohydride species is prominent in formamide based solvents and is critical for the success of theN-formylation reactions. The formoxy borohydride is also found to promote transamidation reactions as a competitive pathway along with reductive functionalization of CO2with amine leading toN-formylation of amines.

Copper catalyzed: N-formylation of α-silyl-substituted tertiary N-alkylamines by air

A site-selective method to prepare N-formyl amines efficiently that relies on the copper(i)-catalyzed oxidation of α-silyl-substituted tertiary N-alkylamines by air at room temperature is described. The oxidative protocol was shown to exhibit excellent functional group tolerance as it was applicable to a wide variety of amine substrates and a number of bioactive molecules and natural products. Moreover, it delinates a ligand-and additive-free amine oxidation process mediated by a low-cost metal salt with oxygen from air taking on the role of both the terminal oxidant and as part of the formylation reagent, which is unprecedented in copper catalysis. It also offers the first synthetic method that can selectively generate α-amino radical species as reactive intermediates from α-silylamines under non-photochemical reaction conditions.

Synthesis of formamides containing unsaturated groups by: N -formylation of amines using CO2 with H2

Formamides have wide applications in the industry and have been synthesized using CO2 as a carbon source and H2 as a reducing agent. However, previous systems required a noble catalyst and high temperature to achieve high efficiency, and the substrate scope was mostly limited to saturated amines. The selective N-formylation of amines containing unsaturated groups using CO2 and H2 is challenging because the efficient catalysts for the N-formylation are usually very active for hydrogenation of the unsaturated groups. Herein, we achieved for the first time a selective and efficient N-formylation of amines containing unsaturated groups using CO2 and H2 with a Cu(OAc)2-4-dimethylaminopyridine (DMAP) catalytic system. The substrates were converted to the desired formamides, while the unsaturated groups, such as the carbonyl group, the CC bond, CN bond and the ester group remained. The main reason for the excellent selectivity of the Cu(OAc)2-DMAP catalytic system was that it was very active for the N-formylation reaction, but was not active for the hydrogenation of the unsaturated groups.

A Titanium Dioxide Supported Gold Nanoparticle Catalyst for the Selective N-Formylation of Functionalized Amines with Carbon Dioxide and Hydrogen

A TiO2-supported, gold nanoparticle catalyst was found to allow the N-formylation of various amines, including normally unreactive anilines, by using CO2 as the carbonyl source under a H2 atmosphere. A series of reducible functional groups, such as olefins, halogens, carbonyls, carbamates, and cyano moieties, were completely retained during the formylation, which proved the highly selective nature of the formylation reaction. The catalyst was also found to be reusable without any loss of activity or selectivity.

Chelating Bis(1,2,3-triazol-5-ylidene) Rhodium Complexes: Versatile Catalysts for Hydrosilylation Reactions

NHC-rhodium complexes (NHC=N-heterocyclic carbenes) have been widely used as efficient catalysts for hydrosilylation reactions. However, the substrates were mostly limited to reactive carbonyl compounds (aldehydes and ketones) or carbon-carbon multiple bonds. Here, we describe the application of newly-developed chelating bis(tzNHC)-rhodium complexes (tz=1,2,3-triazol-5-ylidene) for several reductive transformations. With these catalysts, the formal reductive methylation of amines using carbon dioxide, the hydrosilylation of amides and carboxylic acids, and the reductive alkylation of amines using carboxylic acids have been achieved under mild reaction conditions.

Effective Formylation of Amines with Carbon Dioxide and Diphenylsilane Catalyzed by Chelating bis(tzNHC) Rhodium Complexes

The reductive formylation of amines using CO2 and hydrosilanes is an attractive method for incorporating CO2 into valuable organic compounds. However, previous systems required either high catalyst loadings or high temperatures to achieve high efficiency, and the substrate scope was mostly limited to simple amines. To address these problems, a series of alkyl bridged chelating bis(NHC) rhodium complexes (NHC=N-heterocyclic carbene) have been synthesized and applied to the reductive formylation of amines using CO2 and Ph2SiH2. A rhodium-based bis(tzNHC) complex (tz=1,2,3-triazol-5-ylidene) was identified to be highly effective at a low catalyst loading and ambient temperature, and a wide substrate scope, including amines with reducible functional groups, were compatible. Beyond the norm: Rhodium complexes bearing a strong electron-donating bis(1,2,3-triazol-5-ylidene) ligand were found to be excellent catalysts for the reductive formylation of amines with CO2 and Ph2SiH2 at ambient temperature. The catalyst system possesses a broad substrate scope which tolerates a variety of reducible functional groups and is suitable for the synthesis of bioactive compounds. Tf=trifuoromethanesulfonyl.

Visible-light photo-catalytic C-C bond cleavages: Preparations of N,N-dialkylformamides from 1,2-vicinal diamines

A range of 1,2-vicinal diamines were smoothly converted into N,N-dialkylformamides under the synergistic actions of Ru(bpy) 3Cl2 photo-catalyst, 45 W household lighting bulb, and Cs2CO3 basic additive under very mild reaction conditions. The process involves visible light-enabled photo-catalytic cleavage of C-C bond as the strategic event.

A kinetic study on aminolysis of t-butyl 4-pyridyl carbonate and related compounds: Effect of leaving and nonleaving groups on reaction mechanism

Second-order rate constants kN have been measured spectrophotometrically for nucleophilic substitution reactions of t-butyl 4-pyridyl carbonate 8 with a series of alicyclic secondary amines in H 2O at 25.0 ± 0.1 °C. The Bronsted-type plot for the reactions of 8 is linear with βnuc = 0.84. The βnuc value obtained for the reactions of 8 is much larger than that reported for the corresponding reactions of t-butyl 2-pyridyl carbonate 6 (i.e., βnuc = 0.44), which was proposed to proceed through a forced concerted mechanism. Thus, the aminolysis of 8 has been concluded to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate T±, in which expulsion of the leaving-group from T± occurs at the rate-determining step (RDS). In contrast, aminolysis of benzyl 4-pyridyl carbonate 7 has been reported to proceed through two intermediates, T± and its deprotonated form T- on the basis of the fact that the plots of pseudo-first-order rate constant kobsd vs. amine concentration curve upward. The current study has demonstrated convincingly that the nature of the leaving and nonleaving groups governs the reaction mechanism. The contrasting reaction mechanisms have been rationalized in terms of an intramolecular H-bonding interaction, steric acceleration, and steric inhibition.

Mild, simple, and efficient method for N-formylation of secondary amines via Reimer-Tiemann reaction

A rapid and easy route for the N-formylation of secondary amines using chloroform and sodium ethoxide via dichlorocarbene by the Riemer-Tiemann reaction with excellent yield is reported.

Synthesis and structure-activity relationships of N-aryl-piperidine derivatives as potent (partial) agonists for human histamine H3 receptor

4-((1H-Imidazol-4-yl)methyl)-1-aryl-piperazine and piperidine derivatives were designed and synthesized as candidate human histamine type 3 agonists. The piperazine derivatives were found to have low (or no) affinity for human histamine H3 receptor, where