190841-33-9

Upstream product

• 33686-82-7 1,1'-[(1E)-3-bromoprop-1-ene-1,3-diyl]bis[benzene] 
• 13735-81-4 1-styrenyloxytrimethylsilane 
• 62668-02-4 (E)-1,3-diphenyl-2-propen-1-ol 
• 87751-69-7 rac-(E)-1,3-diphenyl-3-acetoxy-prop-1-ene 
• 100-46-9 benzylamine 
• 100-53-8 phenylmethanethiol 
• 96-09-3 styrene oxide 
• 4663-33-6 1,3-diphenyl-3-hydroxypropene 
• 95-68-1 2,4-Xylidine 
• 100-52-7 benzaldehyde 
• 98-86-2 acetophenone 
• 94-41-7 benzalacetophenone 
• 288-13-1 NH-pyrazole 
• 614-47-1 1,3-diphenyl-propen-3-one 

Downstream Products

• 1357476-14-2 2,4-dimethyl-N-((E)-1,3-diphenylallyl)benzenamine 
• 1357476-02-8 2,4-dimethyl-6-((E)-1,3-diphenylallyl)benzenamine 
• 292639-13-5 (E)-N-(1,3-diphenylallyl)-4-methylbenzenesulfonamide 

Relevant academic research and scientific papers

Carbon-fluorine bond formation via a five-coordinate fluoro complex of ruthenium(II)

The 16-electron, five-coordinate fluoro complex [RuF(dppp)2]PF6 (1a; dppp = propane-1,3-diylbis[diphenylphosphine] smoothly reacts with 1,3- diphenylallyl bromide (=1,1'-(3-bromoprop-1-ene-1,3-diyl)bis[benzne]) in dry CDCl3 to give 1,3-diphenylallyl fluoride and [RuBr(dppp)2]+ in nearly quantitative yield. Under similar conditions, bromide (or chloride)/fluoride exchange also occurs with chlorotriphenylmethane, bromodiphenylmethane, and tert-butyl bromide. The crystal structure of 1a is reported.

Bu4NHSO4-Catalyzed Direct N-Allylation of Pyrazole and its Derivatives with Allylic Alcohols in Water: A Metal-Free, Recyclable and Sustainable System

Allylic amines are valuable and functional building blocks. Direct N-allylation of pyrazole and its derivatives as an atom economic strategy to provide allylic amines has been achieved only using commercial Bu4NHSO4 as the metal-free catalyst and water as the solvent without any additives. 11–93% isolated yields were obtained for the N-allylation of pyrazole and its derivatives with allylic alcohols. Bu4NHSO4 could be reused for six times by simple extraction nearly without loss of catalytic activity and was also suitable for a gram-scale production. The reaction of allylic ether and pyrazole did not occur to give the desired product indicated that allylic ether was not the active intermediate in the pathway. Density functional theory (DFT) calculations reveal that there are hydrogen bonding effects among substrates, solvent and catalyst, especially the one formed between allylic alcohol and H2O. Control experiments in different protic solvents further demonstrate the intermolecular hydrogen bonding of allylic alcohol and water. (Figure presented.).

Bi(OTf)3 catalyzed disproportionation reaction of cinnamyl alcohols

Bi(OTf)3 catalyzed disproportionation reaction of cinnamyl alcohols provides chalcones and benzyl styrenes. The use of various metal triflates is investigated herein for facile and efficient redox transformation. A plausible mechanism has been proposed.

Organocatalytic α-Allylation of α-Branched Aldehydes by Synergistic Catalysis of Br?nsted Acids and Amines

Herein, we describe the first, fully organocatalytic Tsuji–Trost-type direct α-allylation of α-branched aldehydes by the combined use of N-triflyl amides and secondary amines. Aliphatic, aromatic aldehydes as well as allyl alcohols are converted into the

Sulfonic acid-functionalized ionic liquids as metal-free, efficient and reusable catalysts for direct amination of alcohols

A series of sulfonic acid-functionalized (SO3H-functionalized) ionic liquids was synthesized and used as metal-free, highly selective and efficient catalysts for the direct amination of alcohols. Notably, the activities of the series of SO3H-functionalized ionic liquids were compared and a 92% isolated yield was obtained using 3-tetradecyl-1-(butyl-4- sulfonyl)imidazolium trifluoromethanesulfonate ([BsTdIM][OTf]) as the catalyst. Importantly, the catalytic system has wide substrate scope including benzylic, allyl, propargylic, aliphatic alcohols with sulfonamide, amide, carbamate, aromatic amine and N-heterocyclic compounds. Interestingly, the system was also suitable for a multi-gram scale direct amination of alcohols. Additionally, the reusable nature of [BsTdIM][OTf] makes this protocol more attractive and avoids the disposal and neutralization of acidic catalysts. Moreover, preliminary experiments indicated that this reaction should proceed via an SN1 pathway. Copyright

Palladacycle-catalyzed tandem allylic amination/allylation protocol for one-pot synthesis of 2-allylanilines from allylic alcohols

An efficient methodology involving the predominant formation of C-C bonds is described for the first direct synthesis of 2-allylanilines from allylic alcohols via a one-pot tandem allylic amination/ allylation protocol catalyzed by a palladacycle under mild conditions without the requirement for additional activators.

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.

Allylic alkylation and amination using mixed (NHC)(phosphine) palladium complexes under biphasic conditions

A dramatic improvement of the catalytic activity was observed when a phosphine was added in allylic alkylation reactions catalyzed by (NHC)Pd(η3-C3H5)Cl complexes. Consequently, several palladium complexes, generated in situ from different NHC-silver complexes, [Pd(η3-C3H5)Cl]2 and PPh3, were tested in this reaction to evaluate their potential. High reaction rates and conversions could be obtained with this catalytic system in the alkylation of allylic acetates with dimethylmalonate, particularly under biphasic conditions using water/dichloromethane and KOH 1 M as the base. These conditions are experimentally more convenient and gave higher reaction rates than the classical anhydrous conditions (NaH/THF). In this system, the phosphine is essential since no conversion was obtained when it is not present. The steric hindrance of the carbene ligand has a great influence on the activity and the stability of the catalytic system. The best NHC ligands for this reaction are either 1-mesityl-3-methyl-imidazol-2-ylidene or 1-(2,6-diisopropylphenyl)-3-methyl-imidazol-2-ylidene which are less bulky among the NHC tested. These two ligands led in 5 min to a complete conversion at 20 °C. The Pd-catalyzed allylic amination reaction using (E)-1,3-diphenylprop-3-en-yl acetate and benzylamine was also tested with (NHC)(PPh3)Pd complexes and under the biphasic conditions. This reaction was found to be slower than the alkylation with dimethylmalonate but a complete conversion could be reached in 6 h at 20 °C using K2CO3 1 M as the base. NMR experiments indicated that mixed (NHC)(PPh3)Pd complexes are formed in situ but their structure could not be established exactly.

Etherification of (E)-1,3-diaryl- and (E)-1,3-diheteroaryl- prop-2-en-1-ols with primary and secondary alcohols over platinum on carbon

In the presence of platinum on carbon (Pt/C), (E)-1,3-diaryl- and (E)-1,3-diheteroaryl- prop-2-en-1-ols react with primary and secondary alcohols to give (E)-1,3-diaryl- and (E)-1,3-diheteroaryl- prop-2-enyl ethers.

The epoxy-Ramberg-Baecklund reaction (ERBR): A sulfone-based method for the synthesis of allylic alcohols

The epoxy-Ramberg-Baecklund reaction (ERBR) is outlined, in which α,β-epoxy sulfones are converted into a range of mono-, di- and tri-substituted allylic alcohols, on treatment with base. Modification of this method enabled the preparation of enantio-enriched allylic alcohols following the diastereoselective epoxidation of enantio-enriched vinyl sulfones that were accessed efficiently from the chiral pool. The scope, optimisation and limitations of the ERBR as a method for the preparation of allylic alcohols are discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.