92040-02-3

Upstream product

• 110-91-8 morpholine 
• 2327-99-3 1-phenylpropadiene 
• 7217-71-2 1-phenyl-2-propenyl acetate 
• 1826-67-1 vinyl magnesium bromide 
• 120803-36-3 1-morpholino[(phenyl)methyl]benzotriazole 
• 87802-71-9 (E)-methyl cinnamyl carbonate 
• 21040-45-9 Cinnamyl acetate 
• 158662-96-5 trans-3-benzotriazol-1-yl-1-(N-morpholino)prop-1-ene 
• 103-54-8 cinnamyl acetate 

Relevant academic research and scientific papers

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.

Copper-Catalyzed Hydroamination of Allenes: From Mechanistic Understanding to Methodology Development

Experimental and theoretical mechanistic studies on the Cu(OTf)2-catalyzed hydroamination reaction of terminal allenes with secondary amines reveal that in situ generated cationic Cu(I) is the catalytically active species and explain the observ

Ruthenium-catalyzed regio- and enantioselective allylic amination of racemic 1-arylallyl esters

The regio- and enantioselective allylic amination of racemic monosubstituted allylic esters, such as 1-arylallyl acetates, with cyclic secondary amines has been accomplished. The RuCl3/(S,S)-ip-pybox catalyst system has effectively catalyzed th

Palladium catalyzed intermolecular hydroamination of 1-substituted allenes: An atom-economical method for the synthesis of N-allylamines

The palladium complex [(3IPtBu)Pd(allyl)]OTf previously displayed excellent catalytic activity for the hydroamination of 1,1-dimethylallene with anilines, selectively producing the branched substituted allylamine product (kinetic product) in high conversion. In the current report, the scope of this hydroamination reaction has been expanded to include both alkyl amines and anilines in combination with an array of seven alkyl and aryl allenes. For the majority of amines investigated, the hydroamination of 1,1-dimethylallene, cyclohexylallene, benzylallene, and select aryl allenes with alkyl amines gave the branched substituted allylamine product in nearly quantitative conversion at ambient temperature in less than 1 hour. In contrast, anilines displayed a more limited reaction scope and yielded the linear hydroamination product (thermodynamic product) with all allenes other than 1,1-dimethylallene. Both branched and linear products could be formed selectively in the hydroamination of p-fluorophenylallene with alkyl amines through careful control of [(3IPtBu)Pd(allyl)]OTf catalyst loading and reaction duration. Overall, the branched allylamines produced are useful synthetic intermediates due to their available unsaturated vinyl group, while the linear allylamine products are chemically similar to a class of known pharmaceuticals. The Royal Society of Chemistry 2013.

ENANTIOSELECTIVE PHOSPHORAMIDITE COMPOUNDS AND CATALYSTS

This invention relates to phosphoramidite compounds and catalyst complexes which can be used to provide enantioselective reactions including hydroamination reactions, etherification reactions and conjugate addition reactions and allylic substitution reactions, among others. In a first aspect, the present invention is directed to phosphoramidite and related compounds according to general structure (I), where Z is absent or is a group containing O, N or S, preferably O; R1 and R2 are independently an optionally substituted C1-12 alkyl group, an optionally substituted (CH2)n-aromatic group or (CH2)n-heteroaromatic group, or are linked together to form an optionally substituted aliphatic or (CH2)n-aromatic dianion of a diol, diamine, dithiol, aminoalcohol, aminohiolate or a alcoholthiol group; R3’ and R3 are each independently H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic group with the proviso that R3’ and R3 are not both H, or together R3’ and R3 form an optionally substituted C5-C15 saturated or unsaturated carbocyclic ring; R4 is H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic group; R5 is absent, H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic or (CH2)n-heteroaromatic group; Ra and Ra’ are each independently H or a C1-C3 alkyl group, or Ra and Ra’ together with the carbon to which they are attached form a optionally substituted C5-C15 saturated or unsaturated carbocyclic or heterocyclic ring, or an aromatic or heteroaromatic ring; R6 and R7 are each independently H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic group, with the proviso that R5, R6 and R7 cannot simultaneously be H, and when Ra and Ra’, together with the carbon to which they are attached, form a carbocyclic ring, heterocyclic ring or an aromatic or heteroaromatic ring, R5 is absent or is preferably H; R6 and R7 are preferably H or CH3; and each n is independently 0, 1, 2, 3, 4, 5 or 6 and wherein at least one of the carbon atoms attached to the nitrogen of the phosphoramidite group is a chiral center.

Allylic amination via decarboxylative C-N bond formation

This manuscript details the development of a palladium-catalyzed allylic amination that proceeds via decarboxylation of allylic carbamates. Both saturated and aromatic heterocycles undergo decarboxylative rearrangement in good yields. The mechanism of allylation of heteroaromatic amines involves the formation of π-allyl palladium complexes followed by decarboxylation of the carbamate. Finally, the heteroaromatic anion equivalent is allylated to provide allylic amines. Georg Thieme Verlag Stuttgart.

Practical Pd/C-mediated allylic substitution in water

Pd/C-mediated allylic substitution in water is described as an interesting alternative to classical homogeneous conditions. The reaction applied to allylic acetates showed a wide range of compatibility with various nitrogen, sulfur, oxygen, and carbon nucleophiles. Notably, the method features inexpensive reagents and a nontoxic solvent. Moreover, measurement of the palladium content in water by ICP-MS shows low palladium contamination (4 ppm) of the solvent, rendering this method safer for the environment compared to homogeneous conditions. The first asymmetric example of Pd/C-mediated allylic substitution is also disclosed.

Use of a bulky phosphine of weak σ-donicity with palladium as a versatile and highly-active catalytic system: Allylation and arylation coupling reactions at 10-1-10-4 mol% catalyst loadings of ferrocenyl bis(difurylphosphine)/Pd

Carbon-carbon(sp2-sp2 and sp1-sp 2) and carbon-nitrogen (nucleophilic allylation) coupling processes are promoted by a catalytic system containing [PdCl(η3-C 3H5)]2 with the new ferrocenyl bis(difurylphosphine) 1,1′-bis[di(5-methyl-2-furyl)phosphino]ferrocene, Fc[P(FuMe)2]2. Starting from aryl bromides or allylic acetates this versatile catalyst system may be used at low palladium loadings (10-1-10-4 mol%) in some Heck, Suzuki, Sonogashira and allylic amination reactions to give cross-coupled products in excellent yield. Remarkably high activity is obtained in allylic substitution reactions, providing a significant impetus for the development of bulky phosphines possessing weak σ-donicity for this particular reaction.

Supramolecular Catalysts by Encapsulating Palladium Complexes within Dendrimers

Dendrimers are well-defined and highly branched macromolecules. By utilizing their capsular architectures, dendrimers encapsulating various catalytically active species can be prepared, which often bring about unique catalysis. Treatment of the alkylated