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• 541-16-2 t-butyl malonate 
• 87751-69-7 rac-(E)-1,3-diphenyl-3-acetoxy-prop-1-ene 

Relevant academic research and scientific papers

Unsymmetrical terdentate phosphorus-nitrogen-nitrogen (PNN) ligands: Effect of the M/L ratio and the pendant group on stereoselectivity

Twelve novel, unsymmetrical terdentate pyrrolidine-based phosphorus-nitrogen ligands were prepared. These ligands promoted very high catalytic activity in the palladium-catalysed allylic substitution reactions of 1,3-diphenylpropenyl acetate with malonate

P-Chirogenic phosphine/sulfide hybrid ligands

P-Chirogenic phosphine/sulfide hybrid ligands 1 were prepared by the use of optically active phosphine-boranes as the intermediates. The palladium complexes of the ligands exhibited high catalytic activity and enantioselectivity in allylic alkylation of 1-acetoxy-1,3-diphenylprop-2-ene with malonate esters.

Chiral P,Olefin Ligands with Rotamers for Palladium-Catalyzed Asymmetric Allylic Substitution Reactions

We synthesized a series of phosphine-olefin-type chiral aminophosphines, and we confirmed that these each exists as two rotamers at the C(aryl)-N(amine) bond. We also investigated the ability of these aminophosphines to act as chiral ligands for Pd-catalyzed asymmetric allylic substitution reactions, such as the alkylation of allylic acetates with malonates or indoles, and we found they gave high enantio-selectivities (up to 98% ee).

Novel BIPHEN H2 based P,S-bidentate phosphoramidite ligand in palladium-catalyzed asymmetric allylation

The reaction of P,S-phosphoramidite bearing (Ra)-BIPHEN H2 core and exocyclic amino sulfide as the new ligand with [Pd(ppp-allyl)Cl]2 in the presence of AgBF4 yielded a cationic metallochelate [Pd(ppp-allyl)(L)]BF4/s

Formation of Allylpalladium Complexes and Asymmetric Allylation Involving Modular Bridging Diamidophosphite-Sulfides Based on 1,4-Thioether Alcohols

A large family of P,S-bidentate diamidophosphite ligands were readily synthesized from accessible hydroxyl-thioether compounds. One type of Pd(II) cationic allylic complex with these diamidophosphites fulfilling a P-monodentate function, and three types,

Atropselective Dibrominations of a 1,1′-Disubstituted 2,2′-Biindolyl with Diverging Point-to-Axial Asymmetric Inductions. Deriving 2,2′-Biindolyl-3,3′-diphosphane Ligands for Asymmetric Catalysis

On the 1H NMR timescale, 2,2′-biindolyls with (R)-configured (1-alkoxyprop)-2-yl, (1-hydroxyprop)-2-yl, or (1-siloxyprop)-2-yl substituents at C-1 and C-1′ are atropisomerically stable at 30 °C. A 2,2′-biindolyl (R,R)-17 a of that kind and achiral (!) brominating reagents gave the atropisomerically stable 3,3′-dibromobiindolyls (M)- and/or (P)-18 a at best atropselectively—because of point-to-axial asymmetric inductions—and atropdivergently, exhibiting up to 95 % (M)- and as much (P)-atropselectivity. This route to atropisomerically pure biaryls is novel and should extend to other substrates and/or different functionalizations. The dibromobiindolyls (M)- and (P)-18 a furnished the biindolyldiphosphanes (M)- and (P)-14 without atropisomerization. These syntheses did not require the resolution of a racemic mixture, which distinguishes them from virtually all biaryldiphosphane syntheses known to date. (M)- and (P)-14 acted as ligands in catalytic asymmetric allylations and hydrogenations. Remarkably, the β-ketoester rac-25 c was hydrogenated trans-selectively with 98 % ee; this included a dynamic kinetic resolution.

Design of bifunctional chiral phenanthroline ligand with Lewis basic site for palladium-catalyzed asymmetric allylic substitution

Conceptually new bifunctional chiral ligands were developed. The axially chiral N,N-bidentate phenanthroline ligand (S)-1 was found to be effective for Pd-catalyzed asymmetric allylic substitution of allyl acetate and dialkyl malonate. The intramolecular Lewis basic group from the hydroxybinaphthyl structure of (S)-1 played a pivotal role in the high reactivity and enantioselectivity.

Imidate-phosphanes as highly versatile N,P Ligands and their application in palladium-catalyzed asymmetric allylic alkylation reactions

Chiral imidate-phosphanes were developed as a new type of N,P ligands. These ligands are easily accessible through a one-step procedure starting from a commercially available chiral aminophosphane and an imidate precursor. Excellent performance of the cat

Preparation, coordination and catalytic use of planar-chiral monocarboxylated dppf analogues

A novel polar dppf derivative possessing only planar chirality, 1′,2-bis(diphenylphosphino)-ferrocene-1-carboxylic acid (Hdpc), has been synthesised in racemic form and resolved into enantiomers via esters with d-glucose diacetonide ((Rp)- and (Sp)-3). (R p)-Hdpc was further converted to a series of N-substituted amides that were studied as ligands for Pd-catalysed enantioselective allylic alkylation of racemic (E)-1,3-diphenylprop-2-en-1-yl acetate or ethyl carbonate with malonate esters, showing high activity and good enantioselectivity (er up to 10: 90). The catalytic results were correlated with the structural data (X-ray diffraction and solution NMR) for (η3-allyl)palladium(ii) complex (Rp)-[Pd(η3-1,3-Ph2C 3H3){Fe(η5-C5H 3-1-(C(O)NHCH2Ph)-2-(PPh2-κP)) (η5-C5H4PPh2-κP)}]ClO 4 (16) as a model of the plausible reaction intermediate. A further study into the coordination properties of Hdpc led to isolation of chelate complex [PdCl2(Hdpc-κ2P,P′)] (12). The crystal structures of rac-Hdpc, methyl ester of (Rp)-Hdpc, glycoside (R p)-3, and 12·Me2CO suggested a close structural relationship between dppf and Hdpc. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2009.

Development of chiral (S)-prolinol-derived ligands for palladium-catalyzed asymmetric allylic alkylation: Effect of a siloxymethyl group on the pyrrolidine backbone

A series of novel chiral aminophosphine ligands are designed and readily prepared from (S)-prolinol. The reactivity and selectivity in the palladium-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate with a dimethyl malonate-BSA-Li