Synthesis of novel P-ketimine bidentate ferrocenyl ligands with central and planar chirality and comparsion in the catalytic activity between P-ketimine and P-aldimine

A series of novel ferrocenylphosphine-ketimine ligands 6 were prepared by reaction of (R,S-p)-PPFNH2-R or (S,S-p)-PPFNH2 with a variety of m-substituted acetophenones. A different catalytic activity was observed between ferrocenylphosphine-ketimine ligands and corresponding aldimine ligands. The efficiency and diastereomeric impact of these ferrocenylphosphine-ketimine ligands in Pd-catalyzed asymmetric allylic alkylation were first investigated, and higher enantioselectivity of over 98% e.e. with 95% yield was obtained by the use of ferrocenylphosphine-ketimine ligands. However, in Rh-catalyzed asymmetric hydrosilylation of aryl ketones, only 42% e.e. was obtained by the use of ferrocenylphosphine-ketimine ligands compared to 90% e.e. with the use of aldimine ligands. (C) 2003 Elsevier Ltd. All rights reserved.

Rare earth metal alkyl complexes bearing N,O,P multidentate ligands: Synthesis, characterization and catalysis on the ring-opening polymerization of L-lactide

Alkane elimination reactions of rare earth metal tris(alkyl)s, Ln(CH2SiMe3)3(THF)2 (Ln = Y, Lu) with the multidentate ligands HL1-4, afforded a series of new rare earth metal complexes. Yttrium, complex I supported by flexible amino-intino phenoxide ligand HL1 was isolated as homoleptic product. In the reaction of rigid phosphino-imino phenoxide ligand HL 2 with equintolar Ln(CH2SiMe3)3(THF)2, HL 2 was deprotonated by the metal alkyl and its imino C=N group was reduced to C-N by intramolecular alkylation, generating THF-solvated mono-alkyl complexes (2a: Ln = Y; 2b: Ln = Lu). The di-ligand chelated yttriurn complex 3 without alkyl moiety was isolated when the molar ratio of HL 2 to Y(CH,SiMe3)3(THF)2 increased to 2: 1. Reaction of steric phosphino beta-ketoiminato ligand HL 3 with equimolar Ln(CH2SiMe3)3(THF)2 afforded di-ligated mono-alkyl complexes (4a: Ln = Y; 4b: Ln = Lu) without occurrence of intramolecular alkylation or formation of homoleptic product. Treatment of tetradentate methoxy-amino phenol HL 4 with Y(CH2SiMe3)3(THF)2 afforded a monomeric yttrium bis-alkyl complex of THF-free. The resultant complexes were characterized by IR, NMR spectrum and X-ray diffraction analyses.All alkyl complexes exhibited high activity toward the ring-opening polymerization Of L-lactide to give isotactic polylactide with controllable molecular weight and narrow to moderate polydispersity.

Forced extension of P-selectin construct using steered molecular dynamics

P-selectin, a 70-nm-long cellular adhesive molecule, possesses elastic and extensible properties when neutrophils roll over the activated endotheliam of blood vessel in inflammatory reaction. Transient formation and dissociation of P-selectin/ligand bond on applied force of blood flow induces the extension of P-selectin and relevant ligands. Steered molecular dynamics simulations were performed to stretch a single P-selectin construct consisting of a lectin (Lec) domain and an epithelial growth factor (EGF)-like domain, where P-selectin construct was forced to extend in water with pulling velocities of 0.005-0.05 nm/ps and with constant forces of 1000-2500 pN respectively. Resulting force-extension profiles exhibited a dual-peak pattern on various velocities, while both plateaus and shoulders appeared in the extension-time profiles on various forces. The force or extension profiles along stretching pathways were correlated to the conformational changes, suggesting that the structural collapses of P-selectin Lec/EGF domains were mainly attributed to the burst of hydrogen bonds within the major beta sheet of EGF domain and the disruptions of two hydrophobic cores of Lee domain. This work furthers the understanding of forced dissociation of P-selectin/ligand bond.

Preparation of monolithic column and its application in p-CEC

A novel monolithic stationary phase having long alkyl chain ligands was introduced and evaluated in pressurized-capillary electrochromatography of small neutral and charged compounds. The monolithic column was prepared by the in situ copolymerization of ethylene dimethacrylate, 1-hexadecene, allyl alcohol and 2-acrylamido-2-methyl-1-propanesulfonic acid in a quaternary porogenic solvent mixture consisting of 1,4-butanediol, cyclohexanol, dodecanol and water.

Highly enantioselective conjugate addition of diethylzinc to acyclic enones with fine-tunable phosphite-pyridine ligands

A new series of fine-tunable phosphite-pyridine (P,N) ligands derived from (S)-2-amino-T-hydroxy-6,6'-dimethyl-1,1'-biphenyl and (S)-2-amino-2'-hydroxy-4,4',6,6'-tetramethyl-1,1'-biphenyl was employed in Cu(I)-catalyzed conjugate addition of diethylzinc to acyclic enones. Excellent enantioselectivities (up to 98% ee) and highly catalytic activities were achieved for a variety of acyclic enones.

Synthesis of novel ferrocenylphosphine-amidine ligands with central and planar chirality and their diastereomeric effect in Pd-catalyzed asymmetric allylic alkylation

Some novel ferrocenylphosphine-amidine ligands with central and planar chirality were prepared from (R,S-p)-PPFNH2-R 3 and its diastereomer (S,S-p)-PPFNH2 3a. The efficiency and diastereomeric impact of these ferrocenylphosphine-amidine ligands in the palladium-catalyzed asymmetric allylic substitution was examined, and up to 96% e.e. with 98% yield was achieved by the use of ligand (R,S-p)-4a with a methyl group in the amidino moiety. The results also indicated that (R)-central chirality and (S-p)-planar chirality in these ferrocenylphosphine-amidine ligands were matched for the palladium-catalyzed asymmetric allylic alkylation. (C) 2003 Elsevier Ltd. All rights reserved.

Synthesis and characterization of novel neutral nickel complexes bearing fluorinated salicylaidiminato ligands and their catalytic behavior for vinylic polymerization of norbornene

A series of salicylaldimine-based neutral Ni(II) complexes (3a-j) [ArN = CH(C6H40)]Ni(PPh3)Ph [3a,Ar = C6H5; 3b,Ar = C6H4F(o); 3c, Ar = C6H4F(m); 3d, Ar = C6H4F(p); 3e, Ar = C6H3F2(2,4); 3f, Ar = C6H3F2(2,5); 3g, Ar = C6H3F2(2,6); 3h, Ar = C6H3F2(3,5); 3i, Ar = C6H2F3(3,4,5); 3j, Ar = C6H5] have been synthesized in good yield, and the structures of complexes 3a and 3i have been confirmed by X-ray crystallographic analysis. Using modified methylaluminoxane as a cocatalyst, these neutral Ni(II) complexes exhibited high catalytic activities for the vinylic polymerization of norbornene.