6908-73-2

Upstream product

• 123-75-1 pyrrolidine 
• 122-78-1 phenylacetaldehyde 
• 1566-67-2 (Z)-styryl acetate 
• 536-74-3 phenylacetylene 
• 3389-53-5 phenylacetylpyrrolidine 
• 103-80-0 phenylacetyl chloride 
• 39166-25-1 (E)-N-(2-phenylethenyl)morpholine 
• 55606-20-7 (E)-N-styrylpiperidine 
• 82489-29-0 (E)-N,N-diethyl-2-phenylethen-1-amine 
• 100-52-7 benzaldehyde 
• 100-42-5 styrene 
• 103-82-2 phenylacetic acid 

Downstream Products

• 123-75-1 pyrrolidine 
• 3760-54-1 1-pyrrolidinecarboxaldehyde 
• 122-78-1 phenylacetaldehyde 
• 100-52-7 benzaldehyde 
• 115872-74-7 2,4-Diphenyl crotonaldehyde 
• 7206-60-2 1-Phenylazulene 
• 52565-57-8 ethyl 4-phenylpyridine-2-carboxylate 
• 25477-76-3 1,3-Dimethyl-6-phenylpyrazino<2,3-d>pyrimidine-2,4(1H,3H)-dione 
• 546834-43-9 5-(2-hydroxy-benzoyl)-biphenyl-3-carboxylic acid ethyl ester 
• 120-72-9 indole 
• 87-51-4 indole-3-acetic acid 
• 1147864-11-6 3-(diphenylphosphoryl)-2-methyl-4-phenyl-1H-pyrrol-1-ol 

Relevant academic research and scientific papers

B(C6F5)3-catalyzed tandem protonation/deuteration and reduction of: In situ -formed enamines

A highly efficient B(C6F5)3-catalyzed tandem protonation/deuteration and reduction of in situ-formed enamines in the presence of water and pinacolborane was developed. Regioselective β-deuteration of tertiary amines was achieved with high chemo- and regioselectivity. D2O was used as a readily available and cheap source of deuterium. Mechanistic studies indicated that B(C6F5)3 could activate water to promote the protonation and reduction of enamines. This journal is

Selective N1/N4 1,4-Cycloaddition of 1,2,4,5-Tetrazines Enabled by Solvent Hydrogen Bonding

An unprecedented 1,4-cycloaddition (vs 3,6-cycloaddition) of 1,2,4,5-tetrazines is described with preformed or in situ generated aryl-conjugated enamines promoted by the solvent hydrogen bonding of hexafluoroisopropanol (HFIP) that is conducted under mild reaction conditions (0.1 M HFIP, 25 °C, 12 h). The reaction constitutes a formal [4 + 2] cycloaddition across the two nitrogen atoms (N1/N4) of the 1,2,4,5-tetrazine followed by a formal retro [4 + 2] cycloaddition loss of a nitrile and aromatization to generate a 1,2,4-triazine derivative. The factors that impact the remarkable change in the reaction mode, optimization of reaction parameters, the scope and simplification of its implementation through in situ enamine generation from aldehydes and ketones, the reaction scope for 3,6-bis(thiomethyl)-1,2,4,5-tetrazine, a survey of participating 1,2,4,5-tetrazines, and key mechanistic insights into this reaction are detailed. Given its simplicity and breath, the study establishes a novel method for the simple and efficient one-step synthesis of 1,2,4-triazines under mild conditions from readily accessible starting materials. Whereas alternative protic solvents (e.g., MeOH vs HFIP) provide products of the conventional 3,6-cycoladdition, the enhanced hydrogen bonding capability of HFIP uniquely results in promotion of the unprecedented formal 1,4-cycloaddition. As such, the studies represent an example of not just an enhancement in the rate or efficiency of a heterocyclic azadiene cycloaddition by hydrogen bonding catalysis but also the first to alter the mode (N1/N4 vs C3/C6) of cycloaddition.

Revisiting the role of acids and hydrogen bond acceptors in enamine formation

A systematic investigation into the effects of acids and hydrogen bond acceptors on the reaction rates and equilibria of enamine formation is reported. Acids can accelerate the reaction but do not change the reaction equilibria. In comparison, hydrogen bond acceptors facilitate the enamine formation via their strong hydrogen bonding interaction with the water generated in the reaction.

METHOD FOR PRODUCING FLUORINE-CONTAINING COMPOUND

PROBLEM TO BE SOLVED: To provide a method for producing a fluorine-containing compound by the addition reaction of an olefin to a perfluoroalkyl radical, which can be performed industrially in a more suitable manner. SOLUTION: A method for producing a flu

Direct Catalytic Reductive N-Alkylation of Amines with Carboxylic Acids: Chemoselective Enamine Formation and further Functionalizations

Direct reductive N-alkylation of secondary amines with carboxylic acids using molybdenum hexacarbonyl (5 mol %) as catalyst and diethoxymethylsilane as reducing agent generate enamines in a straightforward fashion in high yields. The formed enamines are without the need for isolation or purification further reacted with trimethylsilyl cyanide in the same reaction flask to yield α-amino nitriles in good yields. In the optimized reaction conditions equimolar amounts of carboxylic acid and amine are reacted under neat conditions, and a catalytic amount of trifluoroethanol (0.1 mol %) is added along with TMSCN for the cyanation step. The reductive N-alkylation reaction is demonstrated to be highly chemoselective, tolerating a multitude of different functional groups present in the starting carboxylic acids and amines. The reaction is scalable and the generated α-amino nitriles are converted to other useful compounds, e.g., α-amino acids or amino-tetrazoles. In addition, the intermediate enamines are further transformed into triazolines, sulfonylformamidines, pyrimidinediones, and TMS-propargylamines, respectively, in high yields under mild reaction conditions. Benzoic acids react with secondary amines under similar conditions to give tertiary amines in high yields, and using this methodology, the biologically active compound Piribedil was isolated in 80% yield in a direct one-pot reaction setup.

One-Pot Construction of 1-Phenylchromeno[3,4- b]pyrrol-4(3 H)-one: Application to Total Synthesis of Ningalin B and a Pyrrolocoumarin-Based Electrochromic Switch

An efficient construction of 1-phenylchromeno[3,4-b]pyrrol-4(3H)-one via coupling of 1-styrylpyrrolidine and 4-chloro-3-nitrocoumarin as a key step is reported. This reaction is further applied to the total synthesis of the natural product ningalin B in f

Enamines as Surrogates of Alkene Carbanions for the Reductive Alkenylation of Secondary Amides: An Approach to Allylamines

A new strategy to construct allylamines through reductive alkenylation of secondary amides with enamines is reported. The method features the use of trifluoromethanesulfonic anhydride as an activation reagent of amides, and enamines as unconventional alkenylation reagents. In this manner, enamines serve as surrogates of alkene carbanions instead of the classical enolates equivalents. A possible mechanism involving a Hoffmann-like elimination of the amine-borane complex intermediate is proposed.

Dynamic Covalent Chemistry of Aldehyde Enamines: BiIII- and ScIII-Catalysis of Amine–Enamine Exchange

The dynamic exchange of enamines from secondary amines and enolizable aldehydes has been demonstrated in organic solvents. The enamine exchange with amines was efficiently catalyzed by Bi(OTf)3 and Sc(OTf)3 (2 mol %) and the equilibria (60 mm) could be attained within hours at room temperature. The formed dynamic covalent systems displayed high stabilities in basic environment with 2 % by-product formation within one week after complete equilibration. This study expands the scope of dynamic C?N bonds from imine chemistry to enamines, enabling further dynamic methodologies in exploration of this important class of structures in systems chemistry.

Transformation of Amides into Highly Functionalized Triazolines

Triazoles and triazolines are important classes of heterocyclic compounds known to exhibit biological activity. Significant focus has been given to the development of synthetic approaches for the preparation of triazoles, and they are today easily obtainable through a large variety of protocols. The number of synthetic procedures for the formation of triazolines, on the other hand, is limited and further research in this field is required. The protocol presented here gives access to a broad scope of 1,4,5-substituted 1,2,3-triazolines through a one-pot transformation of carboxamides. The two-step procedure involves a Mo(CO)6-catalyzed reduction of tertiary amides to afford the corresponding enamines, followed by in situ cycloaddition of organic azides to form triazolines. The amide reduction is chemoselective and allows for a wide variety of functional groups such as esters, ketones, aldehydes, and imines to be tolerated. Furthermore, a modification of this one-pot procedure gives access to the corresponding triazoles. The chemically stable amide functionality is demonstrated to be an efficient synthetic handle for the formation of highly substituted triazolines or triazoles.

Mild reductive functionalization of amides into N-sulfonylformamidines

The development of a protocol for the reductive functionalization of amides into N-sulfonylformamidines is reported. The one-pot procedure is based on a mild catalytic reduction of tertiary amides into the corresponding enamines by the use of Mo(CO)6 (molybdenum hexacarbonyl) and TMDS (1,1,3,3-tetramethyldisiloxane). The formed enamines were allowed to react with sulfonyl azides to give the target compounds in moderate to good yields.