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The palladium-catalyzed silylation of aryl chlorides with silylsilatranes proceeds under activator-free conditions; hence, wide functional group compatibility is displayed and boryl and siloxy groups are able to survive. Experimental and computational studies revealed that smooth transmetalation from the silylsilatrane to the arylpalladium chloride is facilitated by strong interaction between the Lewis acidic silicon and the chloride.

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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 alpha-arylation of sterically hindered silyl ketene acetals (SKAs) with sterically hindered aryl bromides occurs efficiently using Pd[P(t-Bu)3]2 as the optimal catalyst and ZnF2 as a promoter. Less sensitive P(t-Bu)3-based catalysts could be also employed but showed a lower activity. The reaction showed a broad scope with regard to both coupling partners, including heteroaryl bromides and cyclic SKAs. It also proved to be scalable to multigram quantities, which allowed us to further transform the ester group and to access conformationally constrained benzyl- and phenethylamines, highly sought-after building blocks for the synthesis of new agrochemicals.

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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 report the reductive elimination of haloarene from {Pd[P(o-tol)3](Ar)(mu-X)}2 (X = Cl, Br, I) upon addition of the strongly electron-donating, but sterically hindered, phosphine P(t-Bu)3and related ligands. Reductive elimination of aryl chlorides, bromides, and iodides from these dimeric arylpalladium(II) halide complexes was observed upon the addition of P(t-Bu)3. Conditions to observe the elimination and addition equilibria were established for all three halides, and values for these equilibrium constants were measured. Reductive elimination of aryl chlorides was most favored thermodynamically, and elimination of aryl iodide was the least favored. However, reactions of the aryl chloride complexes were the slowest. Detailed mechanistic data revealed that cleavage of the starting dimer, accompanied by ligand substitution either before or after cleavage, led to the formation of a three-coordinate arylpalladium(II) halide monomer that reductively eliminated haloarene.

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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 report a palladium-catalyzed method to synthesize acid chlorides by the chlorocarbonylation of aryl bromides. Mechanistic studies suggest the combination of sterically encumbered PtBu3 and CO coordination to palladium can rapidly equilibrate the oxidative addition/reductive elimination of carbon-halogen bonds. This provides a useful method to assemble highly reactive acid chlorides from stable and available reagents, and can be coupled with subsequent nucleophilic reactions to generate new classes of carbonylated products. The Good, the Bad and the Bulky! By employing a sterically encumbered phosphine ligand, tri-tert-butyl phosphine, under palladium catalysis inert aryl bromides are chlorocarbonylated to create reactive acid chlorides by reversible carbon-halogen bond reductive elimination. This general platform allows for an expanded scope of the Heck carbonylation reaction to include previously incompatible 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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Ligand control: The use of Pd complexes containing tBu3P or nitrogen-heterocyclic carbene (NHC) ligands almost completely prevents stereoisomerization, thereby permitting an efficient and selective methylation and higher alkylation of (Z)-2-bromo-1,3-dienes (see scheme, dba = trans,trans-dibenzylideneacetone).

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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 series of CB2-selective agonists containing a benzimidazole core is reported. Design, synthesis, SAR and pharmacokinetic data for selected compounds are described.

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

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Palladium-catalyzed direct C-H arylation of N-iminopyridinium ylides provides a powerful and versatile method for the synthesis of functionalized piperidines in good yields. Chemoselective functionalization of the pyridinium ring in the presence of a pyridine substituent is possible as exemplified by the expedient synthesis of anabasine in 61% overall yield over three steps. 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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Oligo(quinoline-2,3-diyl)s having a terminal bromo group were synthesized by the Suzuki-Miyaura coupling of 5,8-disubstituted 2-bromoquinolin-3-ylboronic acid derivatives, and their helical structures were elucidated by a single-crystal X-ray analysis of the hexamer, UV measurements, and induction of a non-racemic helical sense by introduction of a chiral end group. 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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(Chemical Equation Presented) Piecing them together: The side chains of mycolactones A and B are synthesized with a high degree of stereoselectivity. The components of the side chains are prepared separately, then combined through Pd-catalyzed cross-coupling (see scheme; Z1 = tert- butyldimethylsilyl, Z2 = methoxymethyl, TBAF = tetra-n-butylammonium fluoride).

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Chapter 1 An introduction to palladium catalysis,
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The iterative synthesis of oligoarenes via an organoborane-based cross-coupling reaction (i.e., the Suzuki-Miyaura coupling) has been achieved by using a series of “masked” haloarylboronic acids as building blocks whose ordinarily reactive boronyl groups are temporarily protected by a new masking group derived from 1,8-diaminonaphthalene. Copyright

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