63541-20-8

Upstream product

• 110-91-8 morpholine 
• 103-54-8 cinnamyl acetate 
• 106625-69-8 ethyl (E)-3-phenyl-2-propenyl carbonate 
• 85620-74-2 threo-2-diphenylphosphinoyl-3-morpholino-1-phenylpropan-1-ol 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 696-57-1 N-allylmorpholine 
• 17763-67-6 Phenyl triflate 
• 114893-66-2 threo-2-diphenylphosphinoyl-3-morpholino-1-phenylpropyl dimethyl-t-butylsilyl ether 
• 54664-07-2 1-(2-diphenylphosphinoylethyl)morpholine 
• 2327-99-3 1-phenylpropadiene 
• 673-32-5 1-Phenylprop-1-yne 
• 7217-71-2 1-phenyl-2-propenyl acetate 
• 104-55-2 3-phenyl-propenal 
• 85620-74-2 erythro-2-diphenylphosphinoyl-3-morpholino-1-phenylpropan-1-ol 

Downstream Products

• 19199-41-8 C₁₄H₁₇NO₂ 
• 1321123-18-5 4-methyl-4-cinnamylmorpholinium iodide 

Relevant academic research and scientific papers

Synthesis of dendrimers with a bidentate phosphine core ligand having carboxy groups at the peripheral layer and their application to aqueous media cross-coupling reactions

We prepared a series of dendrimers with a bidentate phosphine core ligand having carboxy groups at the peripheral layer. By employing the corresponding water-soluble dendritic phosphine-palladium complex as a catalyst, the aqueous media Suzuki-Miyaura rea

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.

Palladium-Based Hydroamination Catalysts Employing Sterically Demanding 3-Iminophosphines: Branched Kinetic Products by Prevention of Allylamine Isomerization

A new allylpalladium triflate catalyst with a dimesitylphosphine moiety was synthesized, isolated, and characterized. The greatly increased steric bulk on the phosphine of this palladium catalyst inhibited product isomerization, which is often observed after hydroamination of terminal allenes with secondary amines. The considerably reduced rate of isomerization facilitated the isolation of many previously unknown branched allylamines, products that were inaccessible when using other, more active 3-iminophosphine palladium catalysts.

C-N Bond Formation from Allylic Alcohols via Cooperative Nickel and Titanium Catalysis

Amination of allylic alcohols is facilitated via cooperative catalysis. Catalytic Ti(O-i-Pr)4 is shown to dramatically increase the rate of nickel-catalyzed allylic amination, and mechanistic experiments confirm activation of the allylic alcohol by titanium. Aminations of primary and secondary allylic alcohols are demonstrated with a variety of amine nucleophiles. Diene-containing substrates also cyclize onto the nickel allyl intermediate prior to amination, generating carbocyclic amine products. This tandem process is only achieved under our cooperative catalytic system.

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).

COMPOSITIONS AND METHODS FOR REDUCTION OF KETONES, ALDEHYDES AND IMINIUMS, AND PRODUCTS PRODUCED THEREBY

A method of producing an alcohol, comprises reducing an aldehyde or a ketone with a hydridosilatrane. The reducing is carried out with an activator.

Simple Metal-Free Direct Reductive Amination Using Hydrosilatrane to Form Secondary and Tertiary Amines

This work describes the use of cheap, safe, and easy-to-handle hydrosilatrane as the reductant in direct reductive amination reactions. This efficient method enables a facile, metal-free access to secondary and tertiary amines from a wide range of aldehydes and ketones, with the synthesis of tertiary amines requiring no additives at all. This reaction demonstrates excellent functional group tolerance, chemoselectivity, and scalability. (Figure presented.).

Mitsunobu Reaction Using Basic Amines as Pronucleophiles

A novel protocol for extending the scope of the Mitsunobu reaction to include amine nucleophiles to form C-N bonds through the utilization of N-heterocyclic phosphine-butane (NHP-butane) has been developed. Both aliphatic alcohols and benzyl alcohols are suitable substrates for C-N bond construction. Various acidic nucleophiles such as benzoic acids, phenols, thiophenol, and secondary sulfonamide also provide the desired products of esters, ethers, thioether, and tertiary sulfonamide with 43-93% yields. Importantly, C-N bond-containing pharmaceuticals, Piribedil and Cinnarizine, have been synthesized in one step from the commercial amines under this Mitsunobu reaction system.

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).

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.