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An efficient method for the synthesis of 1-benzyl/arylindazole 2-oxides via a bis(dibenzylideneacetone)palladium(0) [Pd(dba)2]/tert-butyl nitrite (TBN)-catalyzed reaction of o-alkynylaniline derivatives with TBN is reported. The overall transformation involves the formation of three new bonds via N-nitrosation (N?NO), 5-exo-dig cyclization (C?N) and oxidation (C=O). The notable features are the mild reaction conditions, broad substrate scope and dual role of TBN as an NO source and redox co-catalyst. This strategy was implemented for the synthesis of indazole-3-carbaldehyde derivatives and the formal syntheses of pharmaceutically active YC-1, an anticancer agent (lonidamine), and the male contraceptive experimental drugs AF-2785 and adjudin (AF-2364). (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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Bis(cycloocta-1,5-diene)platinum reacts with isopropyl isocyanide to give the trinuclear complex .A related palladium compound was prepared by treating either or with 2,6-dimethylphenyl isocyanide.Reactions of the cluster and its presumed palladium analogue with the olefins (NC)2C:C(CN)2, F2C:CFCl and (CN)2C:C(CF3)2, give the compounds (M=Pt, Pd) in which the metals are eta2-bonded to the coordinated olefins.The compound reacts with F2C:CFBr and with F2C:CFCl to give the traans complexes (X=Br, Cl).Similar compounds (M=Pt, Pd), (L=MeO2CHC:CHCO2Me, <*>OCH:CHCO<*>) have also been prepared, and characterised.Two platinum complexes <2> and (CNC6H3-2,6-Me2)4> have been synthesized by treating the complex with HSiMePh2 and cyclopropenone, respectively.NMR and IR data for the new species are reported and discussed.

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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 cross-coupling of 2-alkylaziridines with alkenylboronic acids to give homoallylamines is presented. The reaction is highly regioselective and stereospecific and provides convenient access to enantioenriched amines with 1,1-disubstituted, 1,2-disubstituted, and trisubstituted alkenes. The modular synthesis of a 2,5-disubstituted pyrrolidine natural product was completed in three steps and 67% overall 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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A method for the allylic alkylation of aminophenol with alkynes was developed using a palladium-catalysed allylation reaction with 100% atom economy. A series of structurally diverse N-allylic substituted allylamines were synthesized in good yields with high chemo-, regio-, and stereoselectivities under mild conditions.

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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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New neutral organometallic palladium(II) complexes, [PdPhI(PNMe2)] (1), [PdPhI(PC=NMe)] (2), [PdPhI(PC=NEt)] (3), and [PdMeCl(PNMe2)] (4), [PNMe2 means N,N-dimethyl-2-(diphenylphosphanyl)aniline; PC=NMe means N-[2-(diphenylphosphanyl)benzylidene]-N-methylamine; PC=NEt means N-[2-(diphenylphosphanyl)benzylidene]-N-ethylamine} have been synthesized by oxidative addition of PhI to [Pd(dba)2] in the presence of the P?N ligand (1-3), or by substitution reaction on [PdMeCl(COD)] with PNMe2 (4). Cationic sigma-organometallic species [PdR(PPh3) (P?N)]+ are obtained upon treating complexes of the type [PdRX(P?N)] with PPh3 and AgCF3SO3 and consist predominantly of the trans-P,P isomer in CDCl3 solution, as shown by NMR spectroscopic studies. The cationic eta3-allyl complex [Pd(eta3-all)(PNMe2)]PF6 has also been prepared and characterized, both in solution and in the solid state. Compounds [PdPhI(PNMe2)] (P21/n), [PdPhI(PC=NMe)] (P1), [PdPhI(PC= NEt)] (P1). and [Pd(eta3-all)(PNMe2)]PF6 (P1) have been authenticated by X-ray analysis.

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

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Gold catalysts have been found to catalyze the tandem assembly of arynes and terminal alkynes efficiently in the presence of CuI under mild reaction conditions to provide useful alkynylated biphenyl derivatives. The Royal Society of Chemistry.

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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 activated alkynes have been used successfully for the first time as the dipolarophile in the palladium-catalyzed asymmetric (3 + 2) cycloaddition, affording highly functionalized cyclopentenes in good to high yields with high chemoselectivities and good to high enantioselectivities. The introduction of an additional carbonyl group at the alpha-position of the alkynyl esters is the key to activating the carbon-carbon triple bond. The reaction process was investigated, and an inverse process of Pd-catalyzed (3 + 2) cycloaddition was observed.

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

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An acylsilane synthesis by a Pd-catalyzed cross-coupling reaction of thiol esters and silylzinc chlorides was developed. S-Phenyl thiol esters with a variety of functional groups were converted to corresponding acylsilanes.

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

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Bis(dibenzylidenacetone)palladium is an efficient and highly selective catalyst for the formation of N-(2,7-dimethylocta-2,7-dienyl)benzoimidazole in the allylation of benzoimidazole with N-(2,7-dimethylocta-2,7-dienyl)-N-methylpiperidinium iodide in the presence of NaH.

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