156382-65-9

Upstream product

• 21040-45-9 Cinnamyl acetate 
• 18424-77-6 sodium diethyl methylmalonate 
• 609-08-5 Diethyl methylmalonate 
• 62116-54-5 sodium diethyl methylmalonate 
• 50555-04-9 cinnamyl benzoate 
• 22023-25-2 1-phenylallyl benzoate 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 4392-24-9 Cinnamyl bromide 
• 7217-71-2 1-phenyl-2-propenyl acetate 
• 21087-29-6 trans-3-phenylprop-2-enyl chloride 

Relevant academic research and scientific papers

Bulky monodentate phosphoramidites in palladium-catalyzed allylic alkylation reactions: Aspects of regioselectivity and enantioselectivity

A series of bulky monodentate phosphoramidite ligands, based on biphenol, BINOL and TADDOL backbones, have been employed in the Pd-catalysed allylic alkylation reaction. Reaction of disodium diethyl 2-methyl malonate with monosubstituted allylic substrates in the presence of palladium complexes of the phosphoramidite ligands proceeds smoothly at room temperature. The regioselectivities observed depend strongly on the leaving group and the geometry of the allylic starting compounds. Mono-coordination occurs when these ligands are ligated in [Pd(allyl)(X)] complexes (allyl=C3H 5, 1-CH3C3H4, 1-C6H 5C3H4, 1,3-(C6H5) 2C3H3; X=Cl, OAc). The solid-state structure determined by X-ray diffraction of [Pd(C3H5)(1)(Cl)] reveals a non-symmetric coordination of the allyl moiety, caused by the stronger trans influence of the phosphoramidite ligand relative to X-. In all of these complexes, the syn,trans isomer is the major species present in solution. Because of fast isomerisation and high reactivity of the syn,cis complex, the major product formed upon alkylation is the linear product, especially for monosubstituted phenylallyl substrates in the presence of halide counterions. In the case of biphenol- and BINOL-based phosphoramidites, however, a strong memory effect is observed when 1-phenyl-2-propenyl acetate is employed as the substrate. In this case, nucleophilic attack competes effectively with the isomerisation of the transient cinnamylpalladium complexes. The asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate afforded the chiral product in up to 93% ee. Substrates with smaller substituents gave lower enantioselectivities. The observed stereoselectivity is explained in terms of a preferential rotation mechanism, in which the product is formed by attack on one of the isomers of the intermediate [Pd{1,3-(C6H5) 2C3H3}(L)-(OAc)] complex.

Schiff bases containing ferrocenyl and thienyl units and their utility in the palladium catalyzed allylic alkylation of cinnamyl acetate

The synthesis and characterization of two new ferrocenyl Schiff bases: [Fc-CH{double bond, long}N-(CH2)n-(C4H3S)] (2) {Fc represents (η5-C5H5)Fe(η5 -C5H4)- and n = 1(2a) or 2(2b)} containing the thienyl (C4H3S) group are reported. NMR studies indicate that 2 have the anti-(E) conformation in solution and the X-ray crystal structure of 2a confirms that it also adopts the anti-(E) form in the solid state. Ligands 2 have been tested in the palladium catalyzed allylic alkylation of (E)-3-phenyl-2-propen-1-yl (cinnamyl) acetate using sodium diethyl 2-methylmalonate as nucleophile. The reaction of 2 with [Pd(η3-1-Ph-C3H4)(μ-Cl)] 2 in the presence of a slight excess K[PF6] produced [Pd(η3-1-Ph-C3H4){Fc-CH{double bond, long}N-(CH2)n-(C4H3S)}] [PF6] {n = 1(5a) or 2(5b)}, which are the intermediates of this catalytic process. NMR studies of 5 reveal the coexistence of several isomers in solution. The stoichiometric reactions of 5 with the nucleophile are also reported. The comparison of the results obtained for 2, [Fc-CH{double bond, long}N-(C6H4-2SMe)] (1a) and [(2,4,6-Me3-C6H2)-CH{double bond, long}N-(C6H4-2SMe)] (1b) has allowed to establish the importance of the nature of the substituents on the imine group on the regioselectivity of the process.

Direct Allylation of Active Methylene Compounds with Allylic Alcohols by Use of Palladium/Phosphine-Borane Catalyst System

The C?C bond formation between active methylene compounds and allylic alcohols has been newly developed by using a palladium complex as a catalyst together with a phosphine-borane ligand. The best phosphine-borane ligand for this direct allylation has bee

Integration of electrooxidative cyclization and chemical oxidation via alkoxysulfonium ions. Synthesis of exocyclic ketones from alkenes with cyclization

An integration of electrooxidative cyclization and chemical oxidation was achieved. Electrochemical oxidation of alkenes having a nucleophilic moiety in the presence of DMSO gave cyclized alkoxysulfonium ions, which were converted to the corresponding ket

Enantioselective total synthesis of (+)-ophiobolin A

The enantioselective total synthesis of (+)-ophiobolin A is described. This total synthesis features the construction of the spiro CD ring of (+)-ophiobolin A through a stereoselective intramolecular Hosomi-Sakurai cyclization reaction, the joining of the

An efficient protocol of indium-catalyzed allylic substitution reaction and its application to polymer synthesis: Complementary regio- and stereoselective allylation polycondensation via Ir and Pd catalyses

An efficient protocol of the Ir-catalyzed allylic substitution reaction is reported using N,O-bis(trimethylsilyl)acetamide as a base in the presence of nBu4NF as a cocatalyst. The reaction completely proceeded under very mild conditions, and a branched allylated compound that is not easy to access via the Tsuji-Trost reaction can be synthesized. The reaction system is practical enough to be applicable for polymer syntheses. The Ir- and Pd-catalyzed allylation polycondensations generally show complementary regio- and stereoselectivities. The Ir-catalyzed reaction is versatile, and a mixed dual regioselectivity such as a branched-linear selectivity on each electrophile can also be achieved. Copyright

Palladium(II)-allyl complexes containing chiral N-donor ferrocenyl ligands

A study of the reactivity of enantiopure ferrocenylimine (SC)-[FcCH{double bond, long}N-CH(Me)(Ph)] {Fc = (η5-C5H5)Fe{(η5-C 5H4)-} (1a) with palladium(II)-allyl complexes [Pd(η3-1R1,3R2-C3H3 )(μ-Cl)]2 {R1 = H and R2 = H (2), Ph (3) or R1 = R2 = Ph (4)} is reported. Treatment of 1a with 2 or 3 {in a molar ratio Pd(II):1a = 1} in CH2Cl2 at 298 K produced [Pd(η3-3R2-C3H4){FcCH{do uble bond, long}N-CH(Me)(Ph)}Cl] {R2 = H (5a) or Ph (6a)}. When the reaction was carried out under identical experimental conditions using complex 4 as starting material no evidence for the formation of [Pd(η3-1,3-Ph2-C3H3){FcC H{double bond, long}N-CH(Me)(Ph)}Cl] (7a) was found. Additional studies on the reactivity of (SC)-[FcCH{double bond, long}N-CH(R3)(CH2OH)] {R3 = Me (1b) or CHMe2 (1c)} with complex 4 showed the importance of the bulk of the substituents on the palladium(II) allyl-complex (2-4) or on the ferrocenylimines (1) in this type of reaction. The crystal structure of 5a showed that: (a) the ferrocenylimine adopts an anti-(E) conformation and behaves as an N-donor ligand, (b) the chloride is in acis-arrangement to the nitrogen and (c) the allyl group binds to the palladium(II) in a η3-fashion. Solution NMR studies of 5a and 6a and [Pd(η3-1,3-Ph2-C3H3){FcC H{double bond, long}N-CH(Me)(CH2OH)}Cl] (7b) revealed the coexistence of several isomers in solution. The stoichiometric reaction between 6a and sodium diethyl 2-methylmalonate reveals that the formation of the achiral linear trans-(E) isomer of Ph-CH{double bond, long}CH-CH2Nu (8) was preferred over the branched derivative (9). A comparative study of the potential utility of ligand 1a, complex 5a and the amine (SC)-H2N-CH(Me)(Ph) (11) as catalysts in the allylic alkylation of (E)-3-phenyl-2-propenyl (cinnamyl) acetate with the nucleophile diethyl 2-methylmalonate (Nu-) is reported.

"Clickphine": A novel and highly versatile P,N ligand class via click chemistry

A novel P,N-type ligand family (ClickPhine) is disclosed that is easily accessible using the Cu(I)-catalyzed azide-alkyne "click" cycloaddition. A diverse set of ligands was made in just three steps from readily available starting materials to give several homogeneous and a heterogeneous catalyst. Preliminary experiments show the efficacy of these ligands in the Pd-catalyzed allylic alkylation reaction.

Transition Metal Catalysis Using Functionalized Dendrimers

Dendrimers are well-defined hyper-branched macromolecules with characteristic globular structures for the larger systems. These novel polymers have inspired many chemists to develop new materials and several applications have been explored, catalysis being one of them. The recent impressive strides in synthetic procedures increased the accessibility of functionalized dendrimers, resulting in a rapid development of dendrimer chemistry. The position of the catalytic site(s) as well as the spatial separation of the catalysts appears to be of crucial importance. Dendrimers that are functionalized with transition metals in the core potentially can mimic the properties of enzymes, their efficient natural counterparts, whereas the surface-functionalized systems have been proposed to fill the gap between homogeneous and heterogeneous catalysis. This might yield superior catalysts with novel properties, that is, special reactivity or stability. Both the core and periphery strategies lead to catalysts that are sufficiently larger than most substrates and products, thus separation by modern membrane separation techniques can be applied. These novel homogeneous catalysts can be used in continuous membrane reactors, which will have major advantages particularly for reactions that benefit from low substrate concentrations or suffer from side reactions of the product. Here we review the recent progress and breakthroughs made with these promising novel transition metal functionalized dendrimers that are used as catalysts, and we will discuss the architectural concepts that have been applied.

Bite angle effect of bidentate P-N ligands in palladium catalysed allylic alkylationf

Two series of new bidentate P-N ligands have been synthesized. Application of these ligands in the palladium catalysed allylic alkylation of crotyl chloride and cinnamyl chloride leads to the preferential formation of the branched product. A larger bite angle of the ligand leads to higher regioselectivity. Stoichiometric alkylation of the complex [Pd(C4H7){p-MeOC6H4C=N(CH 2)4OPPh2}][O3SCF3] proceeds with 88% regioselectivity to the branched product. The Royal Society of Chemistry 2000.