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ASYMMETRIC INDUCTION IN CARBOMETHOXYLATION OF VINYLAROMATICS

A novel carbomethoxylation of vinylaromatics, in particular styrene, which takes place with marked asymmetric induction in the presence of a palladium catalyst and trifluoroacetic acid, is reported.

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

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Photoswitchable Flexible and Shape-Persistent Dendrimers: Comparison of the Interplay between a Photochromic Azobenzene Core and Dendrimer Structure

Two analogous classes of dendrimers with a single azobenzene moiety at the core have been prepared. Flexible benzyl aryl ether dendrimers 1a-e were obtained in good yields by direct alkylation of diphenolic azobenzene 3 with benzyl aryl ether dendrons [G-n]-Br (n = 0-4). In rigid dendrimers 2a-e, the azobenzene configurational switch was linked to phenylacetylene dendrons through acetylenic linkages to maintain the shape-persistent nature of these dendrimers. A comparison of these two different classes of dendrimers with azobenzene cores reveals a difference in the properties of the photochromic moiety upon dendritic incorporation as well as a significant difference in the photomodulation of dendrimer properties. The E ? Z photoisomerization quantum yield decreased markedly with increasing generation for dendrimers 1a-e but only slightly for dendrimers 2a-e. However, increasing generation did not significantly alter thermal isomerization kinetics or activation barriers. The hydrodynamic volumes of azobenzene-containing dendrimers 2b-e were significantly modulated when the azobenzene unit is subjected to irradiation, while those of dendrimers 1b-e were only slightly affected.

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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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Transition metal catalyzed cross-coupling of aryl Grignard reagents with aryl fluorides via Pd- or Ni-activation of the C-F bond: An efficient synthesis of unsymmetrical biaryls – Application of microwave technology in ligand and catalyst screening

Biaryl compounds are prevalent in both nature and in active pharmaceutical ingredients. The palladium and nickel catalyzed cross-coupling of aryl Grignard reagents with aryl fluorides reported herein affords moderate to excellent yields of the corresponding unsymmetrical biaryls. In addition, the first example of a biaryl cross-coupling utilizing unactivated aryl fluorides under phosphine free palladium conditions is reported. Microwave technology allowed rapid optimization of catalyst systems, which identified several ligands for this cross-coupling reaction.

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

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Complexation of N-heterocyclic silylenes to Pd(0): Formationof highly labile homoleptic complexes Pd[Si(tBuNCH2 CH2NtBu]4 and Pd[Si(tBuNCHCHNtBu)]3

The reaction of N-heterocyclic silylenes (NHS) 1 and 2 with Pd complexes, notably [(tert-butyl)3P]2Pd(0) and (COD)Pd(CH3)2, is described. The formation of homoleptic NHS complexes Pd[Si(tBuNCH2CH2NtBu)]4 and Pd[Si(tBuNCHCHNtBu)]3 is reported. The rearrangement of these complexes into dinuclear silylene-bridged compounds and the solid state structures of the latter complexes are discussed.

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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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Rhodium-catalyzed dehydroborylation of styrenes with Naphthalene-1,8- diaminatoborane [(dan)BH]: New synthesis of masked beta-borylstyrenes as new phenylene-vinylene cross-coupling modules

Styrene derivatives underwent dehydroborylation with naphthalene-1,8- diaminatoborane [(dan)BH] in the presence of a cationic rhodium complex, giving beta-borylstyrene derivatives in good yields. Thus prepared beta-borylstyrenes bearing a chlorine or B(pin) group on their aromatic rings were utilized for the synthesis of highly conjugated molecules through stepwise cross-coupling, taking advantage of the dan group as an effective protective group for a boronyl group.

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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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Synthesis, characterization, and reactivity of monomeric, arylpalladium halide complexes with a hindered phosphine as the only dative ligand

We report the isolation and structural characterization of several monomeric arylpalladium(II) halide complexes containing tri-tert-butyl phosphine, 1-adamantyl-di-tert-butylphosphine, or 2-adamantyl-di-tert-butylphosphine. X-ray diffraction, IR spectroscopy, and theoretical studies indicated that the complexes may be stabilized by agostic interactions. For example, the distance from the closest hydrogen atom to the palladium metal center in the X-ray structure of the 1-adamantyl-phenylpalladium bromide complex 1 was 2.26(3) A. The calculated Pd-H distance of 2.28 A and harmonic vibrational frequencies were in agreement with the measured distance, but Wiberg bond indices indicated only weak M-H-C interactions. Addition of 2-adamantyl-di-tert-butyl phosphine to 1 led to ligand exchange and formation of 2-adamantyl-di-tert-butyl phosphine complex 2. Addition of P(t-Bu)3 generated free aryl bromide and Pd[P(t-Bu)3]2. Reactivity of complex 1 with nucleophiles provided evidence of the intermediacy of these complexes in palladium-catalyzed cross-coupling reactions. Complex 1 reacted with amine and base to form the corresponding arylamine, with tert-butoxide to form the corresponding ether, with boronic acid and fluoride to form the corresponding biaryl, and with styrene to form stilbene. This complex also catalyzed the reaction of bromobenzene with diphenylamine in the presence of base to produce 94% of the amination product in 45 min at room temperature. This rate is comparable to the reaction rate of in situ generated catalysts. Copyright

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

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Dialkyl effect on enantioselectivity: pi-Stacking as a structural feature in P,N complexes of palladium(II)

A phosphino, oxazoline P,N-bidentate ligand, 4, containing 3,5-di-tert-butylphenyl groups has been prepared. In the Heck arylation of dihydrofuran, 4 is shown to afford higher ee’s than either 2 or 3, the unsubstituted and m-dimethylphenyl analogues, respectively. Several Pd(0) complexes of 4 are reported. The exchange dynamics of Pd(4)(dba) are shown to involve an interconversion of diastereomers via an intramolecular process. The X-ray structure for PdCl2(4), 8, was determined by X-ray diffraction methods. Comparison of data with PdCl2-(2), 9, and PdCl2(3), 10, suggests that differing amounts of pi-pi stacking influence the structures of these relatively simple Pd complexes, with 9 and 10 revealing the strongest pi-pi interactions. An estimation of the van der Waals energies involved in the interaction supports a ca. 4 kcal/mol stabilization via pi-pi stacking.

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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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Well-defined bisMETAMORPhos PdI-PdI complex: Synthesis, structural characterization, and reactivity

The formation of a bisMETAMORPhos PN-bridged dimeric PdI complex (3) from ligand 1 and Pd(dba)2 is described. The addition of 1 to Pd(dba)2 initially leads to the formation of Pd0 complex 2, which has a highly distorted tetrahedral environment and binds two neutral ligands 1. Complex 2 converts to {PdI}2 complex 3 upon heating. Complex 3 consists of a completely flat Pd-Pd core, with a Pd-Pd bond length of 2.6199(4) A, and the Pd centers display a highly distorted square planar coordination environment. The formation of complex 3 from 2 is suggested to proceed via an in situ comproportionation pathway. Initial decoordination of one ligand from 2 followed by oxidative addition of one neutral coordinated ligand arm leads to a 1-PdIIH complex. Insertion of free dba into the Pd-H bond generates a 1-PdIIdba complex that releases 1,5-diphenylpent-1-en-3-one via intra- or intermolecular protonolysis. Concomitantly, comproportionation with 1-Pd0 yields 3. Complex 3 was found to function as a precatalyst in the Suzuki-Miyaura cross-coupling of p-chloroacetophenone with good conversions.

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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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Because a catalyst decreases the height of the energy barrier, 32005-36-0, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.32005-36-0, Name is Bis(dibenzylideneacetone)palladium, molecular formula is C34H28O2Pd. In a article£¬once mentioned of 32005-36-0

Controllable Si?C Bond Activation Enables Stereocontrol in the Palladium-Catalyzed [4+2] Annulation of Cyclopropenes with Benzosilacyclobutanes

A novel and unusual palladium-catalyzed [4+2] annulation of cyclopropenes with benzosilacyclobutanes is reported. This reaction occurred through chemoselective Si?C(sp2) bond activation in synergy with ring expansion/insertion of cyclopropenes to form new C(sp2)?C(sp3) and Si?C(sp3) bonds. An array of previously elusive bicyclic skeleton with high strain, silabicyclo[4.1.0]heptanes, were formed in good yields with excellent diastereoselectivity under mild conditions. An asymmetric version of the reaction with a chiral phosphoramidite ligand furnished a variety of chiral bicyclic silaheterocycle derivatives with good enantioselectivity (up to 95.5:4.5 er). Owing to the mild reaction conditions, the good stereoselectivity profile, and the ready availability of the functionalized precursors, this process constitutes a useful and straightforward strategy for the synthesis of densely functionalized silacycles.

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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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Synthesis of fused tetracyclic spiroindoles via palladium-catalysed cascade cyclisation

Efficient palladium-catalysed cascade cyclisation to form spiroindoles is developed. Treatment of indoles bearing a propargyl chloride side chain at the 3-position with various external nucleophiles in the presence of a catalytic amount of Pd2(dba)3¡¤CHCl3/dppb and Cs2CO3 in THF gives fused tetracyclic spiroindoles in moderate to good yields.

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