5844-54-2

Upstream product

• 5422-81-1 (E)-3-phenyl-1-(piperidin-1-yl)-prop-2-en-1-one 
• 60-29-7 diethyl ether 
• 110-89-4 piperidine 
• 103-54-8 cinnamyl acetate 
• 103-64-0 bromostyrene 
• 2687-12-9 cinnamyl chloride 
• 5422-81-1 N-(3-phenylpropenoyl)piperidine 
• 85217-69-2 cinnamyl methyl carbonate 
• 104-55-2 3-phenyl-propenal 
• 104-54-1 3-Phenylpropenol 
• 660-88-8 5-aminopentanoic acid 
• 85620-64-0 erythro-2-diphenylphosphinoyl-1-phenyl-3-piperidinopropan-1-ol 
• 54664-06-1 β-Piperidinoethyldiphenylphosphine oxide 
• 4392-24-9 Cinnamyl bromide 

Downstream Products

• 76006-58-1 (E)-4-Phenyl-1-piperidino-3-buten-1-one 
• 104-55-2 3-phenyl-propenal 
• 5422-81-1 N-(3-phenylpropenoyl)piperidine 

Relevant academic research and scientific papers

Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application

Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.

NbCl5-Mg reagent system in regio-and stereoselective synthesis of (2Z)-alkenylamines and (3Z)-alkenylols from substituted 2-alkynylamines and 3-alkynylols

The reduction of N,N-disubstituted 2-alkynylamines and substituted 3-alkynylols using the NbCl5 –Mg reagent system affords the corresponding dideuterated (2Z)-alkenylamine and (3Z)-alkenylol derivatives in high yields in a regio-and stereoselective manner through the deuterolysis (or hydrolysis). The reaction of substituted propargylamines and homopropargylic alcohols with the in situ generated low-valent niobium complex (based on the reaction of NbCl5 with magnesium metal) is an efficient tool for the synthesis of allylamines and homoallylic alcohols bearing a 1,2-disubstituted double bond. It was found that the well-known approach for the reduction of alkynes based on the use of the TaCl5-Mg reagent system does not work for 2-alkynylamines and 3-alkynylols. Thus, this article reveals a difference in the behavior of two reagent systems—NbCl5-Mg and TaCl5-Mg, in relation to oxygen-and nitrogen-containing alkynes. A regio-and stereoselective method was developed for the synthesis of nitrogen-containing E-β-chlorovinyl sulfides based on the reaction of 2-alkynylamines with three equivalents of methanesulfonyl chloride in the presence of stoichiometric amounts of niobium(V) chloride and magnesium metal in toluene.

Iron-Catalysed Reductive Amination of Carbonyl Derivatives with Ω-Amino Fatty Acids to Access Cyclic Amines

An efficient method for the reductive amination of carbonyl derivatives with ω-amino fatty acids catalysed by an iron complex Fe(CO)4(IMes) [IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] by means of hydrosilylation was developed. A variety of pyrrolidines, piperidines and azepanes were selectively synthesised in moderate-to-excellent yields (36 examples, 47–97 % isolated yield) with a good functional group tolerance.

Overcoming solid handling issues in continuous flow substitution reactions through ionic liquid formation

Substitutions such as acylations, arylations, and alkylations are some of the most commonly run reactions for building complex molecules. However, the requirement of a stoichiometric base to scavange acid by-products creates significant challenges when operating in continuous flow due to solid handling issues associated with precipitating base·HX salts. We present a general and simple strategy to overcome these solid handling issues through the use of acid scavenging organic bases that generate low- to moderate-melting ionic liquids upon protonation. The application of these bases towards the most commonly run substitutions are demonstrated, enabling reactions to be run in flow without requiring additional equipment, specific solvents, or dilute reaction conditions to prevent clogging.

A Simple, Broad-Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols

The preparation of allylic amines is traditionally accomplished by reactions of amines with reactive electrophiles, such as allylic halides, sulfonates, or oxyphosphonium species; such methods involve hazardous reagents, generate stoichiometric waste streams, and often suffer from side reactions (such as overalkylation). We report here the first broad-scope nickel-catalysed direct amination of allyl alcohols: An inexpensive NiII/Zn couple enables the allylation of primary, secondary, and electron-deficient amines without the need for glove-box techniques. Under mild conditions, primary and secondary aliphatic amines react smoothly with a range of allyl alcohols, giving secondary and tertiary amines efficiently. This “totally catalytic” method can also be applied to electron-deficient nitrogen nucleophiles; the practicality of the process was demonstrated in an efficient, gram-scale preparation of the calcium antagonist drug substance flunarizine (Sibelium).

Iron-Catalyzed Allylic Amination Directly from Allylic Alcohols

Allylic amination, directly from alcohols, has been demonstrated without any Lewis acid activators using an efficient and regiospecific molecular iron catalyst. Various amines and alcohols were employed and the reaction proceeded through the oxidation/reduction (redox) pathway. A direct one-step synthesis of common drugs, such as cinnarizine and nafetifine, was exhibited from cinnamyl alcohol that produced water as side product. The iron way! A direct amination of allylic alcohols has been demonstrated without the need of Lewis acid activators using an efficient and regiospecific molecular iron catalyst. A range of amines and alcohols were tolerated, and the reaction was found to procced through an oxidation/reduction (redox) pathway (see scheme).

Mild and selective Et2Zn-catalyzed reduction of tertiary amides under Hydrosilylation conditions

Diethylzinc (Et2Zn) can be used as an efficient and chemoselective catalyst for the reduction of tertiary amides under mild reaction conditions employing cost-effective polymeric silane (PMHS) as the hydride source. Crucial for the catalytic activity was the addition of a substoichiometric amount of lithium chloride to the reaction mixture. A series of amides containing different additional functional groups were reduced to their corresponding amines, and the products were isolated in good-to-excellent yields.

Pentacoordinated Carboxylate π-Allyl Nickel Complexes as Key Intermediates for the Ni-Catalyzed Direct Amination of Allylic Alcohols

Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5-cyclooctadiene)2] and 1,1′-bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu4NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu4NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η3-allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.

One-Pot Synthesis of O-Allylhydroxylamines through the Organocatalytic Oxidation of Tertiary Allylic Amines Followed by a [2,3]-Meisenheimer Rearrangement

A cheap, green, and highly efficient one-pot method for the synthesis of O-protected allylic alcohols is described. By utilizing 2,2,2-trifluoroacetophenone as the organocatalyst and H2O2 as the oxidant, a variety of allylic amine N-

Facile synthesis of Z -alkenes via uphill catalysis

Catalytic access to thermodynamically less stable Z-alkenes has recently received considerable attention. These approaches have relied upon kinetic control of the reaction to arrive at the thermodynamically less stable geometrical isomer. Herein, we present an orthogonal approach which proceeds via photochemically catalyzed isomerization of the thermodynamic E-alkene to the less stable Z-isomer which occurs via a photochemical pumping mechanism. We consider two potential mechanisms. Importantly, the reaction conditions are mild, tolerant, and operationally simple and will be easily implemented.