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A highly efficient catalytic system consisting of Pd2(dba)3·CHCl3 and tri(o-tolyl)phosphine has been identified for the coupling of propargylic carbonates with different types of organo boronic acids at room temperature. Excellent central-to-axial chirality transfer was also demonstrated.

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

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Chiral sulfones are of great importance in medicinal chemistry and chemical synthesis. Efficient methods for preparing enantiomerically enriched sulfone-containing molecules can therefore be of significant value; such methods, however, are uncommon. Herein, we report the first general palladium-catalyzed sulfonylation of vinyl cyclic carbonates with sodium sulfinates. A series of enantiomerically enriched tertiary allylic sulfones were synthesized in good yields with excellent enantiomeric ratios. Both aliphatic- and aryl-substituted vinyl cyclic carbonates are suitable reactants with excellent results. This reaction features broad substrates scope, readily available starting materials, excellent regio- and enantioselectivity, and synthesis of sulfone-bearing quaternary carbon stereocenters. Through the sulfonylation of geranyl derived cyclic carbonate 1 h, we achieve the formal total synthesis of (+)-agelasidine A.

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

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We found that the hydrazone-Pd-catalyzed direct intermolecular reaction of o-alkynylphenols with allylic acetates afforded the corresponding 2-substituted-3-allylbenzofuran derivatives. This reaction proceeded smoothly at room temperature using a hydrazone-Pd catalyst system.

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

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The insertion of 1,1-difluoroallenes was carried out to form a C-C bond exclusively on their central carbon. o-Bromophenyl-bearing 1,1-difluoroallenes underwent intramolecular insertion in the presence of a palladium catalyst. Regioselective C-C bond formation occurred to form a six-membered carbocycle, leading to pharmaceutically and agrochemically promising difluoromethylated naphthalenes.

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

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Novel heterodinuclear organopalladium complexes having an unsymmetrical PN ligand (Et2NC2H4PPh2-kappa2N,P)RPd-MLn (MLn = Co(CO)4; R = Me (2a), Ph (2b), MLn = MoCp(CO)3; R = Ph (3b)) are synthesized by metathetical reactions of PdRX(Et2NC2H4PPh2-kappa2N,P) (X = I, NO3) with Na+[MLn]-. Reversible dissociation of the Pd-N bond in 3b is revealed by variable temperature NMR studies. Reactions of 2a and 2b with CO yield corresponding acyl complexes (Et2NC2H4PPh2-kappa2N,P)(RCO)Pd-Co(CO)4 (R = Me (5a), Ph (5b)). Rate of CO insertion for 2a and 2b is significantly faster than those for mononuclear methylpalladium complex, PdMeI(Et2NC2H4PPh2-kappa2N,P) (1a), and methylpalladium-cobalt complex with a 1,2-bis(diphenylphosphino)ethane (dppe) ligand, (dppe-kappa2P,P?)MePd-Co(CO)4 (6a). 5a smoothly reacts with nucleophiles such as diethylamine, methanol and benzenethiol to give corresponding amide, ester and thioester, respectively. These reactions of 5a are also significantly faster than those of corresponding mononuclear analogues and the similar heterodinuclear complexes with symmetrical bidentate ligands such as 1,2-bis(diphenylphosphino)ethane or N,N,N?,N?-tetramethylethylenediamine ligand.

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

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The Pd-catalyzed desulfonative cross-coupling reaction of benzylic sulfone derivatives with 1,3-oxazoles via a deprotonative pathway has been developed. Broad substrate scope for both sulfone and 1,3-oxazole partners is observed, affording a variety of 1,3-oxazole-containing triarylmethanes. Sulfone partners that are primary benzylic, secondary benzylic, and benzhydryl are all effective. Using this method, the straightforward synthesis of multiply arylated structures has been demonstrated.

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

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A method for the in situ generation of ion-paired chiral ligands from simple salts of ammonium phosphines and chiral Bronsted acids under phase-transfer conditions is established. The exploitation of this method in combinatorial ligand screening has enabled the rapid identification of the optimal ion-paired chiral ligand for the palladium-catalyzed asymmetric allylic alkylation of benzo[b]thiophen-2(3H)-ones.

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

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The first asymmetric synthesis of alpha,alpha-disubstituted allylic N-arylamines based on a palladium-catalyzed allylic amination has been developed. The protocol uses highly modular vinyl cyclic carbonates and unactivated aromatic amine nucleophiles as substrates. The catalytic process features minimal waste production, ample scope in reaction partners, high asymmetric induction up to 97% ee, and operational simplicity.

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

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Investigation of the dependence of product enantiometric excess (ee) on catalyst ee is a widely used tool to probe the mechanism of an enantioselective reaction; in particular, the observation of a nonlinear relationship is usually interpreted as an indication of the presence of one or more species that contain at least two units of the chiral entity. In this report, we demonstrate that catalytic enantioconvergent reactions can display an intrinsic negative nonlinear effect that originates purely from the kinetic characteristics of certain enantioconvergent processes and is independent of possible aggregation of the chiral entity. Specifically, this intrinsic negative nonlinear effect can arise when there is a kinetic resolution of the racemic starting material, and its magnitude is correlated with the selectivity factor and the conversion; the dependence on conversion provides a ready means to distinguish it from a more conventional nonlinear effect. We support our analysis with experimental data for two distinct enantioconvergent processes, one catalyzed by a chiral phosphine and the other by a chiral Pd/phosphine complex.

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

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The reaction of alpha-ketoimidoyl chlorides with palladium(0) and platinum(0) derivatives yields trans- (M = Pd; R = p-C6H4OMe, c-C6H11, t-Bu; n = 0,1; M = Pt; R = p-C6H4OMe; n = 1) and cis-, which have been characterized by IR, 1H and 31P NMR spectra and by condensation with MeNH2.

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