201852-22-4

Upstream product

• 100-42-5 styrene 
• 6425-08-7 4,4'-(phenylmethylene)bismorpholine 
• 110-91-8 morpholine 
• 87751-69-7 rac-(E)-1,3-diphenyl-3-acetoxy-prop-1-ene 
• 62668-02-4 (E)-1,3-diphenyl-2-propen-1-ol 

Relevant academic research and scientific papers

A strongly positive dendrimer effect in asymmetric catalysis: Allylic aminations with Pyrphos-palladium functionalised PPI and PAMAM dendrimers

A remarkable and unprecedented increase in catalyst selectivity in dendrimer catalysis is observed for the Pyrphos-Pd catalysed allylic amination of 1,3-diphenyl-1-acetoxypropene as a function of the dendrimer generation (with up to 64 metal sites). This steady increase in ee-values for the allylic amination is less pronounced for the poly(propyleneimine)-derived catalysts than for the corresponding palladium-PAMAM dendrimer catalysts for which an increase in selectivity from 9% ee for a mononuclear reference system to 69% ee for the Pd64-dendrimer was found.

Pickering Emulsion-Derived Liquid-Solid Hybrid Catalyst for Bridging Homogeneous and Heterogeneous Catalysis

We describe a novel method to prepare a liquid-solid hybrid catalyst via interfacial growth of a porous silica crust around Pickering emulsion droplets, which allowed us to overcome the current limitations of both homogeneous and heterogeneous catalysts. The inner micron-scaled liquid (for example, ionic liquids) pool of the resultant catalyst can host free homogeneous molecular catalysts or enzymes to create a true homogeneous catalysis environment. The porous silica crust of the hybrid catalyst has excellent stability, which makes it amenable to packing directly in fixed-bed reactors for continuous flow catalysis. As a proof of concept, the enzymatic kinetic resolution of racemic alcohols, CrIII(salen) complex-catalyzed asymmetric ring opening of epoxides and Pd-catalyzed Tsuji-Trost allylic substitution reactions were used to verify the generality and versatility of our strategy for bridging homogeneous and heterogeneous catalysis. The hybrid catalyst-based continuous flow system exhibited a 1.6a16-fold enhancement in activity relative to homogeneous counterparts even over 1500 h, and the afforded enantioselectivities were completely equal to those obtained in the homogeneous counterpart systems. Interestingly, the catalytic efficiency can be tuned through rational engineering of the porous crust and the dimensions of the liquid pool, resulting in features of an innovatively designed catalyst. This contribution provides a new method to design efficient catalysts that can bridge the conceptual and technical gaps between homogeneous and heterogeneous catalysis.

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.

Water promoted allylic nucleophilic substitution reactions of (: E)-1,3 diphenylallyl acetate

A transition metal free, water based, greener protocol for the allylic alkylation, allylic amination, O-allylation of (E)-1,3-diphenylallyl acetate is described. The developed methodology is applicable for a wide range of nucleophiles furnishing excellent yields of corresponding products up to 87% under mild reaction conditions. A distinct effect of water and base is explored for allylic nucleophilic substitution reactions of (E)-1,3-diphenylallyl acetate.

Micellar catalysis using a photochromic surfactant: Application to the pd-catalyzed tsuji-trost reaction in water

The first example of a Pd-catalyzed Tsuji-Trost reaction, applied in a photochromic micellar media under conventional heating and microwave irradiation, is reported. The surfactant activity and recycling ability were investigated and compared with those of a few commercially available surfactants. The synthetic photochromic surfactant proved to be efficient, recyclable, and versatile for Pdcatalyzed coupling reactions.

Palladium-catalyzed vinylation of aminals with simple alkenes: A new strategy to construct allylamines

A novel, highly selective palladium-catalyzed vinylation reaction for the direct synthesis of allylic amines from styrenes and aminals has been established. The utility of this method was also demonstrated by the rapid synthesis of cinnarizine from aldehydes, amines, and simple alkenes in one-pot manner. Mechanistic studies suggested that the reaction proceeds through a valuable cyclometalated Pd(II) complex generated by the oxidative addition of aminal to a Pd(0) species.

Catalytic materials based on catalysts containing ionic liquid phase supported on chitosan or alginate: Importance of the support

Catalysts containing an ionic liquid phase immobilised on chitosan or alginate supports are successfully applied to the palladium catalysed allylation and amination reactions. The influence of the chemical structure of the support not only on the activity

Allylic amination using well-defined [(NHC)Pd(?3-allyl)Cl] complexes and PPh3

The allylic amination reaction catalyzed by [(NHC)Pd(allyl)-Cl] complexes has been studied, and the presence of PPh3found to be essential for the catalytic system to be active. [(1-Mesityl-3-methylimidazol-2-ylidene)Pd(?3- C3H5)Cl] hasbeen used to optimize the conditions of the reaction with (E)-1,3-diphenylprop-3-enyl acetate and benzylamine under bi-phasic conditions (aqueous base/CH2Cl2). The best yields ofisolated product (98%) were obtained using aqueous 1 MK2CO3. The influence of the NHC ligand and the allyl frag-ment on the pre-catalyst was also examined. Two new neu-tral [(NHC)Pd(?3-1-RC3H4)Cl] complexes [NHC = 1-mesityl-3-methylimidazol-2-ylidene or 1-(2,6- diisopropylphenyl)-3-methylimidazol-2-ylidene; R = H or Ph] have been preparedand a decrease of the reaction time observed with the former. NMR studies have shown that this pre-catalyst is more easilyactivated than its ?3-allyl analogue and that the predominantactivation pathway involves attack of the amine at the allyl fragment. This reaction occurs exclusively in the presence ofPPh3, thus suggesting that cationic [(NHC)Pd(allyl)(PPh3)] +complexes, which are more electrophilic, are formed in situand allow the amine to react with the allyl fragment. A tetra-fluoroborate cationic complex has therefore been preparedfrom [(NHC)Pd(allyl)Cl], PPh3, and AgBF4 and fully charac-terized. This complex is an active pre-catalyst in the allylicamination reaction. The scope of the reaction was examinedunder the optimized reaction conditions with several dif-ferent nitrogen nucleophiles and allylic acetates. The amin-ation products were obtained in yields ranging from 73 to 98%, except for that from cyclohexenyl acetate and diben-zylamine. Finally, the reaction performed directly with theallylic alcohol and benzylamine led to a mixture of allylicamines in 9% yield. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009.

Silyl-modified Bellus-Claisen rearrangement

A silyl-modified variant of the Bellus-Claisen rearrangement is described; the generality of this rearrangement has been demonstrated with a range of allylic amines and ketenes. The Royal Society of Chemistry.

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.