88057-04-9

Upstream product

• 95190-90-2 (2S)-(4-phenylbut-3-en-2-yl) N-phenylbenzimidate 
• 108-59-8 malonic acid dimethyl ester 
• 82045-04-3 (rac)-(E)-2-acetoxy-4-phenylbut-3-ene 
• 62413-47-2 (2R,3E)-4-phenyl-3-buten-2-ol 
• 591-50-4 iodobenzene 
• 1313878-08-8 (S,E)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-3-en-2-yl acetate 
• 18424-76-5 sodiodimethylmalonate 
• 122-57-6 1-Phenylbut-1-en-3-one 
• 81176-43-4 (S)-4-phenyl-but-3-en-2-ol 
• 18424-76-5 dimethyl malonate sodium salt 
• 100017-26-3 (R)-(Z)-3-acetoxy-1-phenyl-1-butene 
• 121232-23-3 (+)-(R)-(E)-(4-phenyl-3-buten-2-yl) (diphenylphosphino)acetate 

Downstream Products

• 1310827-45-2 dimethyl 2-methyl-2-((E)-4-phenylbut-3-en-2-yl)malonate 

Relevant academic research and scientific papers

Palladium-catalyzed enantioselective allylic substitution in the presence of monodentate furanoside phosphoramidites

A library of monodentate furanoside phosphoramidites, easily synthesized from inexpensive D-xylose and optically pure 1,1-bi-2-naphthol (BINOL), was used as ligands for the palladium-catalyzed allylic alkylation and amination. The matched pair was formed from D-xylose-derivatives and (S)-BINOL. The asymmetric induction depends strongly on the substituent at the C5 of the carbohydrate backbone; both bulky 5-O-pivaloyl and 5-deoxy derivatives gave excellent results, whereas ligands with trityl protection at position C5 induced low ee values with reversal of configuration. The solvent used for the addition is also of great importance with highest enantioselectivities observed in diethyl ether. The best results for both alkylation and amination, up to 98-99 ee, were obtained for sterically demanding allylic acetates. Single is better: New carbohydrate ligands bearing a single 1,1-bi-2-naphthol (BINOL)-derived phosphoramidite moiety are developed and successfully applied to the palladium-catalyzed asymmetric allylic substitution. The enantioselectivities are equal or better than those obtained for similar systems containing two BINOL moieties and reach up to 99 ee.

Highly enantioselective alkylation of allyl acetates using tartrate-derived bioxazoline ligands

Tartrate-derived bioxazoline ligands, which form a five-membered chelate ring with metals, were evaluated for use in the asymmetric allylic alkylation (AAA) reactions of various symmetrical and unsymmetrical allyl acetates. Excellent enantioselectivities

Novel O,N,N,O-tetradentate ligand from tartaric acid

A new class of highly stable O,N,N,O-tetradentate bioxazoline ligands were synthesized from l-tartaric acid. Exploration of those ligands in Pd-catalyzed asymmetric allylic alkylation yielded alkylated product up to 96% ee. Necessity of additional chelation to obtain high enantioselectivity was also demonstrated. Structural modifications of this ligand might result in identification of a novel privileged chiral ligand from an inexpensive chiral pool.

Achieving chemo-, regio-, and stereoselectivity in palladium-catalyzed reaction of γ-borylated allylic acetates

Three-carbon highly functionalized γ-borylated allylic acetates underwent a regio- and stereocontrolled Tsuji-Trost reaction in the presence of palladium complexes. An ipso substitution of the acetate with complete stereoretention of the chiral center was achieved, leading to vinylic boronates with enantiomeric excesses above 99%.

Effective chiral ferrocenyl phosphine-thioether ligands in enantioselective palladium-catalyzed allylic alkylations

Chiral ferrocene-derived phosphine-thioether mixed donor ligands supported by heterocycles effected the palladium-catalyzed enantioselective allylic alkylations with excellent yields and enantioselectivities (up to 96% ee). With cyclic and unsymmetrical a

A highly regioselective salt-free iron-catalyzed allylic alkylation

(Chemical Equation Presented) Ironing out the kinks: A highly regioselective allylic alkylation can be performed in the presence of catalytic amounts of an iron(-II) complex and triphenylphosphane (see scheme; EWG = electron-withdrawing group). Allyl carbonates and pronucleophiles are coupled in high yields with a high regioselectivity comparable only with that obtained with Rh catalysts. The reaction is broadly applicable and does not require external base.

Palladium complexes with chiral diphospholane ligands: Comparative catalytic properties and analysis of (η3-allyl)palladium species

The chiral diphospholane ligands Duphos (1) and Duxantphos (2), which can be differentiated by their bite angle, were applied to palladium-catalysed asymmetric reactions, essentially allylic alkylations with symmetrically (3a-d) or unsymmetrically (5a,b) substituted allylic acetates as substrates. The most interesting results were found with the first series of substrates in which 2 was more reactive and/or selective than 1. The model complexes of the catalytic intermediates [Pd{(S,S)-1}(η3-cyclohexenyl)](BF4) (10) and exo-[Pd{(R,R)-(η3-cyclohexenyl)](SbF6) (11) could be characterised by X-ray crystallography. 1H and 32P NMR spectroscopic analyses of [Pd{(R,R)-2}(η3-diphenylallyl)] (SbF6) (12) and [Pd{(R,R)-2}(η3-allyl)](SbF 6) (13) revealed the presence of exchanging isomers in solution. Structural data provided by these techniques combined with the preferential rotation model led to a satisfactory interpretation of the catalytic allylic alkylation results. It appears that the bite angle plays a crucial role in the positioning of the proximal methyl groups, which determines the distribution of allyl isomeric intermediates and the balance between clockwise and anticlockwise rotations in the enantioselective step. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Synthesis and application of chiral cyclopropane-based ligands in palladium-catalyzed allylic alkylation

A series of chiral, cyclopropane-based phosphorus/sulfur ligands have been synthesized and evaluated in the palladium-catalyzed allylic alkylation of 1,3-diphenylpropenyl acetate with dimethyl malonate. Variation of the ligand substituents at phosphorus,

Stereochemistry of the palladium-catalyzed allylic substitution: The synanti dichotomy in the formation of (π-allyl)palladium complexes and their equilibration

The mechanism of palladium(0)-catalyzed allylic substitution has been investigated with the aim of finding whether or not the intermediate (π-alryl)palladium complexes can arise in a syn fashion as an alternative to the well known anti-mechanism. Using (diphenylphosphino)acetate as a leaving group and stereochemically biased substrates 30b and 35b evidence for the syn stereochemistry has been acquired (30b → 31 and 35b → 36). This reversal of stereochemistry is facilitated by severe steric congestion in the starting allylic esters (which impairs the ordinary anti-mechanism) and is boosted by the pre-coordination of the Pd(0) reagent to the leaving group. The latter effect apparently lowers the activation entropy. With cyclohexene derivatives 10b, 18b, and 19b and acyclic substrate 25b, where steric hindrance does not operate, the anti-mechanism producing η3-complexes dominates even for (diphenylphosphino)acetates. At elevated temperature, rapid equilibration of η3-complexes (13 ? 14 and 20 ? 21) has been observed prior to the reaction with a nucleophile. This effect has been attributed to the presence of (diphenylphosphino)acetate ion acting as a ligand for palladium.