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Exploiting the modularity of ion-paired chiral ligands for palladium-catalyzed enantioselective allylation of benzofuran-2(3 H)-ones

A highly enantioselective allylation of benzofuran-2(3H)-ones is achieved under Pd catalysis by taking full advantage of the structural modularity of ion-paired chiral ligands.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Lariat ethers with fluoroaryl side-arms: A study of CF…metal cation interaction in the complexes of N-(o-fluoroaryl)azacrown ethers

New lariat ethers, N-(o-fluorophenyl)aza-15-crown-5 (F-A15C5) and N,N?-bis(o-fluorophenyl)diaza-18-crown-6 (F2-A 218C6), were prepared by the N-arylation of the corresponding azacrown ethers. The interaction of the ligands with metal cations was studied in solution by 1H and 19F NMR (in acetone-d6) and UV spectroscopy (MeOH) confirming the formation of complexes of F 2-A218C6 with K+, Na+, Ag +, Ba2+, Pb2+ and of F-A15C5 with Na + and giving evidence of CF…metal cation interaction. Cation binding constants (beta, evaluated by UV titration method), demonstrate that F-A15C5 and F2-A218C6 form more stable complexes than their fluorine-free analogs. The effect depends on the nature of the metal cation and is at a maximum for hard, singly charged cations (up to 3 logbeta units for K+ complex of F2-A218C6). The X-ray structures of complexes [Pb(F2-A218C6)(H 2O)](ClO4)2 (1) and [Ba(F2-A 218C6)(ClO4)2] (2) reveal short Pb-F (2.805 A) and Ba-F (2.965 A) contacts. Complex 2 is centrosymmetric (C i), while complex 1 has C2 symmetry with one-side coordination of o-fluorophenyl groups to Pb2+. This “one-side” coordination mode of Pb2+ is indicative of a partial localization of the Pb2+ lone pair.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Self-adaptable catalysts: Substrate-dependent ligand configuration

Pd(II) allyl and Pd(0) olefin complexes containing the configurationally labile ligand 1,2-bis-[4,5-dihydro-3H-dibenzo[c-e]azepino]ethane were studied as models for intermediates in Pd-catalyzed allylic alkylations. According to NMR and DFT studies, the ligand prefers Cs conformation in both eta3-1,3-diphenylpropenyl and eta3-cyclohexenyl Pd(II) complexes, whereas in Pd(0) olefin complexes it adopts different conformations in complexes derived from the two types of allyl systems in both solution and, as verified by X-ray crystallography, in the solid state. These results demonstrate that the Pd complex is capable of adapting its structure to the reacting substrate. The different structural preferences also provide an explanation for the behavior of 1,3-diphenyl-2-propenyl acetate and 2-cyclohexenyl acetate in Pd-catalyzed allylic alkylations using pseudo-C 2 and pseudo-Cs symmetric ligands.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Palladium-catalyzed regio- and diastereoselective tandem silastannylation/allyl addition of allene aldehydes and allene ketones: Synthesis of cis cyclopentanols and cyclohexanols

Two in one: the palladium-catalyzed regio- and diastereoselective silastannylation of allene aldehydes and ketones and the subsequent allyl addition to the carbonyl group gives rise to cis-cycloalkanols (see scheme; n = 1, 2; R = H, CH3; X = NTs, O, C(CO2Et)2, etc.). This tandem process requires a single catalyst and is carried out at a constant temperature.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Novel (oxazolinyl)phenyl phosphinite pincer ligand: Development of the first non-symmetrical, PCN type chiral palladium and platinum complexes

Chiral palladium and platinum complexes bearing non-symmetrical, PCN pincer ligand, 6-methoxy-3-(4?-isopropyl-2?-oxazolin-2?-yl)phenyl diphenylphosphinite [i-Pr-Phemox-OPPh2], are first synthesized via oxidative addition of (i-Pr-Phemox-OPPh2)Br 6 to Pd 2(dba)3 ? (CHCl3) or Pt(dba)2 and subsequent treatment with silver salts.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Trimetallic FePd2 and FePt2 4-ferrocenyl-NCN pincer complexes

Ferrocene-bridged NCN pincer complexes of structural type Fe(eta5-C5H4-4-NCN-1-MX)2 (X = I: 6, M = Pd; 7, M = Pt; X = Cl: 8, M = Pt; NCN = [4-C6H2(CH2NMe2)2 -2,6]-) are accessible by the subsequent reaction of Fe(eta5-C5H4-4-NCNH)2 (4) with nBuLi and [PtCl2(SEt2)2] (synthesis of 8) or treatment of Fe(eta5-C5H4-4-NCN-1-I)2 (5) with [Pd2(dba)3] (synthesis of 6) or [Pt(tol)2(SEt2)]2 (synthesis of 7) (dba = dibenzylidene acetone, tol = 4-tolyl). In addition, the Sonogashira cross-coupling of Fe(eta5-C5H4I)2 (1) with HC{triple bond, long}C-4-NCNH (2) gives Fe(eta5-C5H4-C{triple bond, long}C-4-NCNH)2 (3). The reaction behavior of 3 towards tBuLi is reported as well. Cyclovoltammetric studies show that the ferrocene entity can be oxidized reversibly. The Fe(II)/Fe(III) potential decreases with increasing electron density at the NCN pincer units due to the presence of the M-halide moiety (M = Pd, Pt). The solid state structure of Fe(eta5-C5H4-4-NCN-1-PdI)2 (6) is presented. In 6 the Fe(eta5-C5H4)2 unit connects two NCN-PdI pincer entities with palladium in a square-planar environment. The cyclopentadienyl ligands show a staggered conformation. The C6H2 rings are tilted by 23.5(3) towards the C5H4 entities and the C6H2 plane is almost coplanar with the PdN2ipso CI coordination plane (10.3(3)).

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Enantioselective synthesis of sterically hindered alpha-allyl-alpha-aryl oxindoles: Via palladium-catalysed decarboxylative asymmetric allylic alkylation

The highly enantioselective synthesis of sterically hindered alpha-allyl-alpha-aryl oxindoles possessing an all-carbon quaternary stereocenter at the oxindole 3-position has been developed. The key step in the synthetic route employed was a novel one-pot, two-step synthesis of alpha-aryl-beta-amido allyl ester substituted oxindoles in good yields of 41-75% (13 examples) by interception of an unstable allyl ester intermediate through reaction with aryllead triacetate reagents. Pd-Catalyzed decarboxylative asymmetric allylic alkylation (DAAA) was optimized with 2,4,6-trimethoxyphenyl as the aryl-containing substrate. A screen of chiral P,N- and P,P-based ligands showed that the ANDEN-phenyl Trost ligand was the most effective, affording the corresponding alpha-allyl-alpha-aryl oxindole product in 96% yield and 99% ee. A substrate scope of a further 12 alpha-aryl-beta-amido allyl ester substituted oxindoles showed that products containing bulky di-ortho-methoxy substituted arenes and naphthyl groups were formed in very high ee’s (94-98%), whereas those lacking this substitution pattern were formed in more moderate levels of enantioselectivities (56-63% ee). Surprisingly, the 2,6-dimethylphenyl-substituted substrate afforded the O-allylated product in contrast to the expected C-allylated product. A crystal structure was obtained of the 2,4,6-trimethoxyphenyl-substituted alpha-allyl-alpha-aryl oxindole product which enabled us to identify the absolute stereochemistry of the quaternary stereocenter formed. A plausible explanation to rationalise the sense of enantioselection observed in these DAAA transformations is also proposed.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A Highly Warped Heptagon-Containing sp2 Carbon Scaffold via Vinylnaphthyl pi-Extension

A new strategy is demonstrated for the synthesis of warped, negatively curved, all-sp2-carbon pi-scaffolds. Multifold C?C coupling reactions are used to transform a polyaromatic borinic acid into a saddle-shaped polyaromatic hydrocarbon (2) bearing two heptagonal rings. Notably, this Schwarzite substructure is synthesized in only two steps from an unfunctionalized alkene. A highly warped structure of 2 was revealed by X-ray crystallographic studies and pronounced flexibility of this pi-scaffold was ascertained by experimental and computational studies. Compound 2 exhibits excellent solubility, visible range absorption and fluorescence, and readily undergoes two reversible one-electron oxidations at mild potentials.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Asymmetric Allylic Alkylation of Alkanoic-Acid Ester Enolates

A protocol for the direct palladium-catalyzed asymmetric allylic alkylation of simple alkanoic-acid esters through their lithium enolates has been developed. The method permits to create stereogenic centers in the homo-allylic or allylic position. The configuration of the allylation products has been elucidated.

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Unexpected bond activations promoted by palladium nanoparticles

Thioether-phosphines, 1 and 2, were applied for the stabilisation of palladium nanoparticles (PdNPs) synthesised by a bottom-up methodology, using [Pd2(dba)3] as an organometallic precursor. For the phenyl containing ligand 1, small (dmean = 1.6 nm), well-defined and dispersed nanoparticles were obtained; however, ligand 2 involving a long alkyl chain led to agglomerates. NMR and GC-MS analyses throughout the synthesis of the nanomaterials revealed partial cleavage of ligands by C-S and C-P bond activations, and XPS spectra of the isolated nanoparticles indicated the presence of both thioether-phosphines and their fragments on the metallic surface. Reactivity studies of molecular palladium systems as well as on extended palladium surfaces pointed out that cluster entities are responsible for C-heteroatom activations, triggering structure modifications of stabilisers during the synthesis of PdNPs. the Partner Organisations 2014.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method