New explortion of Tris(dibenzylideneacetone)dipalladium-chloroform

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Convenient synthetic routes to enantiomerically pure 1?,2?, 3?,4?,5?-pentamethyl and -pentaphenylferrocenyl imidazolines are described. While the former complexes were diastereoselectively ortho-lithiated and subsequently functionalized by trapping with various electrophiles, the latter complexes could be diastereoselectively cyclopalladated, allowing the preparation of the first enantiomerically pure ferrocenyl palladacycles bearing C5Me5 or C 5Ph5 spectator ligands. The planar chiral palladacycles have been shown to be promising catalysts for aza-Claisen rearrangement reactions of allylic trifluoroacetimidates.

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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 tandem protocol for the synthesis of cyclopentene fused heterocycles from diazabicyclic alkenes and ortho-functionalized aryl iodides has been elaborated. This tandem protocol was utilized for the synthesis of a number of cyclopentene fused dihydrobenzofurans and indolines. The reaction can be tuned toward the formation of either 3,4-disubstituted cyclopentenes or cyclopentene fused heterocycles by careful manipulation of the reaction parameters. The reaction was also extended to bicyclic alkenes derived from fulvene, which resulted in the heteroannulation of the azabicyclic 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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A palladium catalyst generated from Pd2(dba)3*CHCl3 and n-Bu2PCH2CH2Py (Py = 2-pyridyl) has effected novel cycloaddition of methoxyallene with CO2 to afford (E)-5-methoxy-2-(methoxy-methylene)-4-methylene-5-pentanolide regio- and stereospecifically, where a methoxy functional group plays an important role.

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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 general methodology for the synthesis of enantioenriched tertiary allylic aryl ethers through Pd-catalyzed decarboxylative reactions of vinyl cyclic carbonates and phenols is presented. Switching of the regioselectivity toward the formation of linear products by a judicious choice of the ligand is also reported.

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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 describe the development of a new method to use palladium catalysis to form functionalized aromatics: via the metathesis of covalent sigma-bonds between Ar-X fragments. This transformation demonstrates the dynamic nature of palladium-based oxidative addition/reductive elimination and offers a straightforward approach to incorporate reactive functional groups into aryl halides through exchange reactions. The reaction has been exploited to assemble acid chlorides without the use of high energy halogenating or toxic reagents and, instead, via the metathesis of aryl iodides with other acid chlorides.

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

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Nitrile-functionalized NCN-pincer complexes of type [MBr(N{triple bond, long}C-4-C6H2(CH2NMe2)2-2,6)] (6a, M = Pd; 6b, M = Pt) (NCN = [C6H2(CH2NMe2)2-2,6]-) are accessible by the reaction of Br-1-N{triple bond, long}C-4-C6H2(CH2NMe2)2-2,6 (2b) with [Pd2(dba)3 · CHCl3] (5a) (dba = dibenzylidene acetone) and [Pt(tol-4)2(SEt2)]2 (5b) (tol = tolyl), respectively. Complex 6b could successfully be converted to the linear coordination polymer {[Pt(N{triple bond, long}C-4-C6H2(CH2NMe2)2-2,6)](ClO4)}n (8) upon its reaction with the organometallic heterobimetallic pi-tweezer compound {[Ti](mu-sigma,pi-C{triple bond, long}CSiMe3)2}AgOClO3 (7) ([Ti] = (eta5-C5H4SiMe3)2Ti). The structures of 6a (M = Pd) and 6b (M = Pt) in the solid state are reported. In both complexes the d8-configurated transition metal ions palladium(II) and platinum(II) possess a somewhat distorted square-planar coordination sphere. Coordination number 4 at the group-10 metal atoms M is reached by the coordination of two ortho-substituents Me2NCH2, the NCN ipso-carbon atom and the bromide ligand. The N{triple bond, long}C group is para-positioned with respect to M.

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

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Catalytic C-phenylation of methyl acrylate to methyl cinnamate with the Ph4SbX complexes (X = F, Cl, Br, OH, OAc, O2CEt) in the presence of the palladium compounds PdCl2, Pd(OAc)2, Pd2(dba)3, Pd(Ph3P)2Cl2, and Pd(dppf)Cl2 (dba is dibenzylideneacetone and dppf is bis(diphenylphosphinoferrocene)) was studied in organic solvents (MeCN, THF, DMF, MeOH, and AcOH). The highest yield of methyl cinnamate (73% based on the starting organometallic compound) was obtained for the Ph4SbCl- PdCl2 (1:0.04) system in acetonitrile.

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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 dual strategies of cascade cyclocarbopalladation/cross-coupling of alkynes and a reductive Heck reaction have been developed to construct dibenzo[c,f]oxocine frameworks with tri- and tetra-substituted exo-cyclic alkenes with high stereo- and regio-control. The success of this efficient methodology has been demonstrated by the synthesis of a number of dibenzoxocines in moderate to good yields and in sufficient quantities to support their further development.

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

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Five- and six-membered nitrogen and oxygen heterocycles are accessible from two acyclic precursors in a one-pot reaction that comprises a Ru-catalyzed eneyne addition followed by a Pd-catalyzed asymmetric allylic alkylation (see scheme). The stereochemistry of the products derives from the catalyst rather than from substrate control using chiral substrates.

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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 borylstannane [-N(Me)CH2CH2(Me)N-]B-SnMe 3 is a superior reagent capable of effecting bisfunctionalization- cyclization in several highly functionalized 1,n-diynes, 1,n-enynes, and 1,n-allenynes (including 1,2-dipropargylbenzenes, 2,2?- dipropargylbiphenyls, 4,5-dipropargyldioxolanes, and 1,4-dipropargyl-beta- lactams) where the more well-known silylstannanes fail. Variable-temperature NMR studies showed that conformational restraints imposed by selected backbones increase the activation barrier for the helical isomerization in (Z,Z)-dienes that are generated in the cyclization of the diynes. In the biphenyl and dioxolane systems, the reactions proceed with surprisingly good regio-and stereoselectivity. The resulting diazaborolidine derivatives are hydrolytically unstable but can be isolated by recrystallization or precipitation. For further synthetic applications, it is advantageous to convert these compounds in situ into the corresponding dioxaborolidines with either retention of the Me 3Sn group or replacement of this group via halodestannylation. The configurations of the vinyl moieties are preserved in these reactions. Highly functionalized dibenzocyclooctadienes, which adorn the carbon frames of several important cytotoxic natural products, can be synthesized using this chemistry.

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