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The Pd-catalyzed decarboxylative allylation of alpha-(diphenylmethylene) imino esters (1) or allyl diphenylglycinate imines (2) is an efficient method to construct new C(sp3)-C(sp3) bonds. The detailed mechanism of this reaction was studied by theoretical calculations [ONIOM(B3LYP/ LANL2DZ+p:PM6)] combined with experimental observations. The overall catalytic cycle was found to consist of three steps: oxidative addition, decarboxylation, and reductive allylation. The oxidative addition of 1 to [(dba)Pd(PPh 3)2] (dba=dibenzylideneacetone) produces an allylpalladium cation and a carboxylate anion with a low activation barrier of +9.1 kcal mol-1. The following rate-determining decarboxylation proceeds via a solvent-exposed alpha-imino carboxylate anion rather than an O-ligated allylpalladium carboxylate with an activation barrier of +22.7 kcal mol -1. The 2-azaallyl anion generated by this decarboxylation attacks the face of the allyl ligand opposite to the Pd center in an outer-sphere process to produce major product 3, with a lower activation barrier than that of the minor product 4. A positive linear Hammett correlation [rho=1.10 for the PPh3 ligand] with the observed regioselectivity (3 versus 4) supports an outer-sphere pathway for the allylation step. When Pd combined with the bis(diphenylphosphino)butane (dppb) ligand is employed as a catalyst, the decarboxylation still proceeds via the free carboxylate anion without direct assistance of the cationic Pd center. Consistent with experimental observations, electron-withdrawing substituents on 2 were calculated to have lower activation barriers for decarboxylation and, thus, accelerate the overall reaction rates. Copyright

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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 PdLn (n = 3, L = PtBuPh2; n = 2, L = PtBu2Ph, PtBu3, PCy3) with CS2 in hexanes results in precipitation of either Pd(eta2-(CS2)L2 (L = PtBuPh2, PCy3) or Pd2(mu-CS2)2L2 (L = PtBu2Ph, PtBu3).The monomeric complexes Pd(CS2)L2 are unstable in CS2 solution and convert to the corresponding doubly CS2-bridged dimeric complexes Pd2(CS2)2L2.It is the steric bulk of the phosphine ligands that appears to control which type of product initially precipitates.Reaction of the trinuclear clusters Pd3(CO)3L3 with CS2 gives the dimeric complexes Pd2(CS2)2L2.The molecular structure of Pd2(CS2)2(PtBu2Ph)2 has been determined by a single crystal X-ray analysis.Crystals of the complex are monoclinic, space group P21/c (a 10.373(2), b 13.684(1), c 12.173(2) Angstroem, beta 94.04(7) deg) with two centrosymmetrically related dimers per unit cell.The final agreement indices (172 variables, 2071 reflections) are R = 0.032 and Rw = 0.038.The PPd(CS2)2PdP core is essentially planar with each CS2 ligand ?-bonded through the C=S linkage to one metal atom and ?-bonded to the other through the second S-atom.

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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 new range of polar imidazolium and phosphate-containing ligands was synthesised from readily available starting materials in high yielding multi-step transformations. These ligands were used to generate Pd catalysts for Suzuki and Heck C?C coupling reactions in organic and organic/aqueous media. The catalysts performed well in aqueous media in the Suzuki reaction and less well in the Heck reaction, related to substrate solubility in the aqueous media. When moving to ionic liquids, the Heck reaction dramatically improved, especially in media compatible with the polar catalysts and the non-polar reagents. In all cases, the catalysts were stable to the formation of Pd black, a form of degradation that frequently befalls Pd catalysts. The catalysts could be successfully recycled without loss of activity.

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

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Supporting information for this article is given via a link at the end of the document. By intercepting the acylpalladium species with C=N bond of azaarenes or imines other than free amines or alcohols, the difunctionalization of C=N bond was established via palladium-catalyzed carbonylation/nucleophilic addition sequence. This method is compatible with a diverse range of azaarenes and imines and allows for the efficient synthesis of a wide range of quinazolinones and derivatives. The synthetic utility has been demonstrated by one-step synthesis of evodiamine and its analogue with inexpensive starting materials.

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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 use of an isolatable, monomeric Pd(I) complex as a catalyst for the oxidative cross-coupling of aryl-antimony and aryl-boron nucleophiles is reported. This reaction tolerates a wide variety of substrates, with >20:1 selectivity for cross-coupled products. This strategy offers a new approach to achieving the selective cross-coupling of nucleophiles.

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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 preparation of the polyketide natural products anguinomycin C and D is reported based on key steps such as Negishi stereoinversion cross coupling, Jacobsen Cr(III)-catalyzed Hetero Diels – Alder reaction, Evans B-mediated syn-aldol chemistry, and B-alkyl Suzuki – Miyaura cross coupling. The configuration of both natural products was established as (5R,10R,16R,18S,19R, 20S). Biological evaluation demonstrated that these natural products are inhibitors of the nuclear export receptor CRM1, leading to shutdown of CRM1-mediated nuclear protein export at concentrations above 10 nM. Analogues of anguinomycin and leptomycin B (LMB) have been prepared, and the simple alpha,beta-unsaturated lactone analogue 4 with a truncated polyketide chain retains most of the biological activity (inhibition above 25 nM). The structural basis for this inhibition has been demonstrated by modeling the transport inhibitors into X-ray crystal structures, thus highlighting key points for successful and strong biological action of anguinomycin and LMB.

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

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After decades of development, carbonylation reactions have become one of the most powerful tools in modern organic synthesis. However, the requirement of CO gas limits the applications of such reactions. Reported herein is a versatile and practical protocol for carbonylative reactions which rely on the cooperation of phenyl formate and nonaflate, and the generation of CO in situ. This protocol has a high functional-group tolerance and could be applied in carbonylations with C, N, and, O nucleophiles. The corresponding amides, alkynones, furanones, and aryl benzoates were synthesized in good yields. Transformers: A versatile and practical protocol for carbonylation reactions involve the cooperation of phenyl formate and nonaflate with generation of CO in situ. This protocol has a high functional-group tolerance and could be applied in carbonylative couplings with C, N, and O nucleophiles. The corresponding amides, alkynones, furanones, and aryl benzoates were synthesized in good yield.

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

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(Chemical Equation Presented) Split and run: A study of the asymmetric hydrogenolysis of an aryl-carbon-bromine bond in a naphthalene chromiumtricarbonyl complex shows the use of a new bulky phosphoramidite ligand to yield the product in highly enantiomerically enriched form (see scheme).

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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 NCN palladium(II) pincer complex [Benzoyl(NACAN)PdBr] (16) was synthesized by the oxidative addition of Benzoyl(NACAN)Br to Pd(dba)2 in 85% yield [(NACAN) = 5-tert-butyl-1,3-bis(N-substituted benzimidazol-2′-yl)phenyl)]. Then treatment of complex 16 with KI yielded the iodopalladium complex [Benzoyl(NACAN)PdI] (17) in 92% yield. Furthermore, a series of cationic palladium(II) complexes, including [Benzoyl(NACAN)Pd(MeCN)]+[BF4]-(18), [Benzoyl (NA CA N) Pd (MeC N)] + [S b F 6]-(19), a n d [Benzoyl(NACAN)Pd(OTf)] (20), were prepared in 68-79% yields by the reaction of the neutral palladium(II) complex (16) with AgBF4, AgSbF6, and AgOTf, respectively. Similarly, previously synthesized Tosyl(NACAN)PdBr [5-tert-butyl-1,3-bis(N-tosylbenzimidazol-2?-yl)phenyl]palladium bromide (5b) was treated with AgSO3CF3 and AgSbF6 to afford cationic palladium(II) complexes [Tosyl(NACAN)Pd(OTf)] (21) and [Tosyl(NACAN)Pd-(MeCN)]+[SbF6]-(22) in 41 and 61% yields, respectively. 5-tert-Butyl-1,3-bis[{(N-tosylbenzimidazol-2?-yl)phenyl}palladium-(II)] triflate (21) exhibited an unsupported metallophillic Pd???Pd interaction [3.166(8) A] that is corroborated by X-ray crystallographic studies. Compared to other cationic palladium complexes, complex 21 was found to be less stable. In Atoms in Molecule (AIM) analysis, the bond critical point (A) between Pd and Pd atoms is 0.000865 au, supporting the presence of metallophillic interaction in complex 21. The bond strength of the Pd???Pd bond was also measured by density functional theory calculations that indicated that the calculated bond order was approximately one-fourth of the normal covalent Pd-Pd bond (natural atomic orbital bond order method). All eight complexes, two neutral and six cationic, were characterized by common spectroscopic techniques, and six complexes were corroborated by X-ray diffraction studies.

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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 steric bulk of the phosphane ligand determines the mechanism of the ArX addition to zero-valent [PdL2] complexes. This effect has been studied by variation of ligands (catalyst: [Pd(PCxntBu3-n)2]; n=0-3, Cx = cyclohexyl) in Pd couplings of unsaturated electrophiles, and different reaction pathways (A= associative, B =dissociative) identified, depending on the size of the ligand.

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