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Cyclization of 4-hydroxy-2-pyrones with allylic bisacetates by a palladium catalyst is described. Pyrone-annulated 2-oxabicyclo[3.3.1]nonane derivatives were regioselectively produced from the reaction of 4-hydroxy-2-pyrones with 1,4-diacetoxy-2-cyclohexene at high temperature. The reaction would proceed via a migration of the pi-allylpalladium intermediate.

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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 example of highly enantioselective intramolecular hydroarylation of allyl aryl ethers was realized by palladium-catalyzed reductive heck reactions utilizing a new chiral sulfinamide phosphine ligand (N-Me-XuPhos). N-Me-XuPhos can be easily prepared on gram scale from readily available starting materials in a one-pot synthesis approach. A series of optically active 2,3-dihydrobenzofurans bearing a quaternary stereocenter were obtained in good yields and with excellent enantioselectivities. The practicality of this reaction was validated in the straightforward synthesis of CB2 receptor agonists. Moreover, deuterium was efficiently incorporated into the products.

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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 cycloisomerization of enynes catalyzed by Pd(OAc)2 and bis-benzylidene ethylenediamine (bbeda) is a landmark methodology in transition-metal-catalyzed cycloisomerization. However, the mechanistic pathway by which this reaction proceeds has remained unclear for several decades. Here we describe mechanistic investigations into this reaction using enynamides, which deliver azacycles with high regio- and stereocontrol. Extensive 1H NMR spectroscopic studies and isotope effects support a palladium(II) hydride-mediated pathway and reveal crucial roles of bbeda, water, and the precise nature of the Pd(OAc)2 pre-catalyst. Computational studies support these mechanistic findings and lead to a clear picture of the origins of the high stereocontrol that can be achieved in this transformation, as well as suggesting a novel mechanism by which hydrometalation proceeds.

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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 palladium-catalyzed oxa-[4+2] annulation of para-quinone methides with allyl carbonates bearing a nucleophilic alcohol side chain has been developed. This method provided an efficient strategy to the construction of 2-oxaspiro-cyclohexadienones via 1,6-conjugated addition-mediated allylation in moderate to good yields. Preliminary results on asymmetric derivatives promised potential in the synthesis of enantioenriched frameworks. (Figure presented.).

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

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Dinuclear Pd(I) and Pt(I) complexes bridged by (dimethylphosphinomethyl)dimethylamine (mm-pcn), 2>, were prepared.X-Ray crystal structure analysis revealed that the Pd complex is a head-to-tail isomer in which the two coordination planes around Pd are coplanar.

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

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Get selective! Enantioselective allylation of ketimines derived from isatins by using chiral 1,3-bis(imidazolin-2-yl)benzene (Phebim)-PdII complexes afforded products with good enantioselectivity (see scheme). The reaction was applied to a wide variety of ketimines. The obtained product can be converted to homoallylic amines and a spirocyclic amine without the loss of enantiopurity. 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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Palladium(0)-catalyzed carbocyclization of 1,7-enynes mediated by (chlorodimethylsilyl)pinacolborane proceeds with 1,8-addition of the silicon and boron functions to give functionalized cyclohexane derivatives with boron attached to the exocyclic olefin. A variety of chromane dervatives are accessible by this method. In contrast to the analogous reactions with 1,6-enynes, the configuration of the newly formed stereogenic center is controlled by a stereogenic center present in the substrate.

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

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2H-Chromene is an important structural motif that exists in natural products and non-natural compounds possessing interesting biological activities. In this investigation, a highly efficient approach toward 2H-chromenes has been developed based on palladium-catalyzed coupling of N-tosylhydrazones and beta-bromostyrenes. The mechanism of this reaction is proposed that involves the formation of vinyl palladium by carbene migratory insertion and the intramolecular nucleophilic substitution. This journal is

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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 here a novel method for the modular synthesis of highly substituted piperazines and related bis-nitrogen heterocycles via a palladium-catalyzed cyclization reaction. The process couples two of the carbons of a propargyl unit with various diamine components to provide nitrogen heterocycles in generally good to excellent yields and high regio- and stereochemical control. (Chemical Equation Presented).

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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 3-tert-butyl-1-(stannylpropyl)-functionalized cyclopentadienyl ligand precursor 6 is readily available in 64% overall yield from allylic alcohol 1 by a three-step reaction sequence including Pd-catalyzed hydrostannylation with Ph3SnH. Treatment with FeCl2 and ZrCl4 · 2THF afforded corresponding ferrocene and zirconocene derivatives. Transmetallation of Sn-Ph with Li-Bu was observed under these reaction conditions by using BuLi as a base.

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