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An efficient palladium-catalyzed cascade reaction of azides with isonitrile and amines is presented; it offers an alternative facile approach toward N -sulfonyl-, N -phosphoryl-, and N -acyl-functionalized guanidines in excellent yield. These series of substituted guanidines exhibit potential biological and pharmacological activities. In addition, the less reactive intermediate benzoyl carbodiimide could be isolated by silica gel column flash chromatography in moderate 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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The invention relates to compounds of formula (I) and salts thereof, formula (I) wherein the substituents are as defined in the specification, the application of a compound of formula (I) in a process for the treatment of the human or animal body, in particular with regard to C-Met tyrosine kinase mediated disease; the use of a compound of formula (I) for manufacturing a medicament for the treatment of such diseases; pharamaceutical compositions comprising a compound of the formula (I), optionally in the presence of a combination partner; processes for the preparation of a compound of formula (I).

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

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Zinc methyl 20-substituted 31-demethyl-bacteriopheophorbides-d were prepared through palladium-catalyzed cross-coupling of chlorophyll-a derivatives. The synthetic zinc 31-hydroxy-131-oxo-chlorins possessing a(n) (un)substituted ethynyl or butadiynyl group at the 20-position were good models for bacteriochlorophylls-c/d found solely in chlorosomes, the main light-harvesting antennas of green photosynthetic bacteria. Similarly as in natural chlorosomes, the synthetic models self-aggregated in an aqueous Triton X-100 solution to form large oligomers with red-shifted and broadened electronic absorption bands. While a phenyl group directly connected with the chlorin pi-system at the 20-position disturbed the chlorosomal self-aggregation, the insertion of an ethynylene group between the two functional groups reduced the steric hindrance around the 20-position and was useful for the facile formation of the self-aggregates. A similar substitution effect was observed in the 20-ethynyl to butadiynyl moieties bearing a sterically bulky trimethylsilyl group at the terminal position.

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

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Ethynyl-bridged porphyrin-corrole dyads and triads were synthesized by using Pd(0) mediated coupling reactions and their structures were characterized by NMR, FT-IR, UV/Vis and fluorescence techniques. Besides spectroscopic techniques, computational studies at B3LYP/6-311G(d,p) level of DFT were also used to elucidate the minimum energy geometries and the molecular orbital characteristics of the new dyads and triads. DFT calculations pointed out the presence of charge separated donor-acceptor property between macrocycles of dyads and triads, and the emission studies indicated an excited state interaction between macrocycles, and energy transfer from the porphyrin to the corrole unit.

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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 herein the first examples of a palladium-catalyzed enantioselective Cacchi reaction for the synthesis of indoles bearing a chiral C2-aryl axis. In the presence of a catalytic amount of Pd(OAc)2 and (R,R)-QuinoxP* ligand, reaction of N-aryl(alkyl)sulfonyl-2-alkynylanilides with arylboronic acids under oxygen atmosphere afforded enantioenriched 2,3-disubstituted indoles in high yields and enantioselectivity. The indole ring is constructed de novo in this process and a complexation-induced chirality transfer is proposed to account for the observed enantioselectivity.

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

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Far-red (FR)/near-infrared (NIR) photosensitizer is highly desirable in image-guided photodynamic cancer therapy. Herein, a new conjugated polymer of poly(1,2-bis(4-((6-bromohexyl)oxy)phenyl)-1,2-diphenylethene-co-alt-9,10-anthraquinone) (PTPEAQ) consisting of tetraphenylethylene (TPE), an iconic aggregation-induced emission (AIE) active group as the electron donor, and anthraquinone (AQ) as the acceptor, is prepared for the first time through one-pot Suzuki polymerization. Encapsulation of PTPEAQ with a block copolymer followed by surface functionalization with anti-Her2 affibody yields PTPEAQ-NP-HER2. It shows bright AIE-active FR/NIR emission and efficient singlet oxygen generation under visible light irradiation, which has been successfully used for photodynamic cancer cell ablation using SKBR-3 cells, a type of breast cancer cell with HER2 overexpression on cell membrane, as an example.

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

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Novel bidentate ligands of general formula (I) are described Formula (I): R represents a hydrocarbyl aromatic structure. The substituent(s) Yx on the aromatic structure has a total X=1-n SigmatYx of atoms other than hydrogen such that x-1-nSigmatYx is ? 4, where n is the total number of substituent(s) Yx and tYx represents the total number of atoms other than hydrogen on a particular substituent Yx. The groups X1, X2, X3 and X4 are joined to Q1 or Q2 via tertiary carbon atoms to the respective atom Q1 or Q2; and Q1 and Q2 each independently represent phosphorus, arsenic or antimony. A catalyst system and a process for the carbonylation of ethylenically unsaturated compounds utilising the catalyst system is also 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 cross coupling reaction engaging N-tosylhydrazones of corresponding ketones as a nucleophilic coupling partner and various alkenyl tosylates and mesylates as an electrophiles for the synthesis of various alkenyl derivatives. The salient features of this reactions are (1) no stoichiometric organometallic reagents required, (2) it tolerates a wide range of functional groups, (3) easy to handle and required mild conditions. 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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C3-alkenylated and C3-(hetero)arylated 1H-indazoles are privileged structural motifs in numerous pharmaceuticals. Direct C3-alkenylation and C3-(hetero)arylation of 1H-indazoles have been significantly challenging because of the inert nature of this carbon center. Herein, we present an efficient mechanochemical strategy for palladium-catalyzed C-H/C-H cross-coupling to construct C3-alkenylated and C3-heteroarylated 1H-indazoles using low-cost copper oxidants with satisfactory product yields and broad functional group tolerance. The robustness of the developed protocols was further demonstrated by the unprecedented total mechanosynthesis of the intermediate of PLK4 inhibitor CFI-400945 and HIF-1alpha inhibitor YC-1.

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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 method for the synthesis of benzoxepines via migratory insertion into a Pd carbene followed by C-C bond cleavage was developed. Various benzoxepines were constructed by the regioselective ring expansion concomitant with the introduction of an aryl group at their 5-position.

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