4.4. Pd on Modified Silica 159 4.5. Pd on Clay and Other Inorganic Materials 159 5. Stille, Fukuyama, and Negishi Reactions 159 5.1. Stille Reactions 159 5.1.1. Pd on Carbon (Pd/C) 159 5.1.2. Palladium on KF/Al2O3 159 5.1.3. Pd on Modified Silica (SiO2/TEG/Pd) 159 5.2. Fukuyama Reactions 159 5.2.1. Pd on Carbon (Pd/C) 159 5.2.2. Pd(OH)2 on Carbon (Perlman’s Catalyst) 160 5.3. Pd/C-Catalyzed Negishi Reactions 160 6. Ullmann-Type Coupling Reactions 161 6.1. Pd/C-Catalyzed Aryl−Aryl Coupling 161 6.2. Pd/C-Catalyzed Homocoupling of Vinyl Halides 162

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Chem.%20Rev/Chem.%20Rev.%202007,%20107,%20133-173.pdf

Carbon-Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium Catalysts

Practical methodologies for the synthesis of indoles.

A surface science perspective on TiO2 photocatalysis

Since the discovery of organic azides by Peter Griess more than 140 years ago, numerous syntheses of these energy-rich molecules have been developed. In more recent times in particular, completely new perspectives have been developed for their use in peptide chemistry, combinatorial chemistry, and heterocyclic synthesis. Organic azides have assumed an important position at the interface between chemistry, biology, medicine, and materials science. In this Review, the fundamental characteristics of azide chemistry and current developments are presented. The focus will be placed on cycloadditions (Huisgen reaction), aza ylide chemistry, and the synthesis of heterocycles. Further reactions such as the aza-Wittig reaction, the Sundberg rearrangement, the Staudinger ligation, the Boyer and Boyer-Aube rearrangements, the Curtius rearrangement, the Schmidt rearrangement, and the Hemetsberger rearrangement bear witness to the versatility of modern azide chemistry.

Organic Azides: An Exploding Diversity of a Unique Class of Compounds

https://chemistry.mdma.ch/hiveboard/rhodium/pdf/archive/merbst/quinoline1999.pdf

Quinoline, quinazoline and acridone alkaloids

Co I I -porphyrin complexes catalyze the reaction of aromatic azides (ArN 3 ) with hydrocarbons that contain a benzylic group (ArR 1 R 2 CH) to give the corresponding amines (ArR 1 R 2 C-N-HAr). When at least one of the R substituents is hydrogen, the catalytic reaction proceeds further to give the imine ArRC=NAr in good yields. The reaction mechanism has been investigated. The reaction proceeds through a reversible coordination of the arylazide to the Co I I - porphyrin complex. This unstable adduct can either react with the hydrocarbon in the rate-determining step or decompose by a unimolecular mechanism to afford a putative "nitrene" complex, which reacts with more azide, but not with the hydrocarbon, to afford the byproduct diaryldiazene. The kinetics of the catalytic reaction have been investigated for a range of azides and substituted toluenes. Arylazides with electron-withdrawing substituents react at a faster rate and a good correlation is found between the log(k) and the Taft parameters. On the other hand, an excellent correlation between the logarithm of the rate for substituted toluenes relative to that of toluene and a radical parameter (σ . J J ) alone was found, with no significant contribution by polar parameters. An explanation has been proposed for this anomalous effect and for the very high isotopic effect (k H /k D = 14) found.

Amination of benzylic C-H bonds by arylazides catalyzed by CoII-porphyrin complexes: a synthetic and mechanistic study.

High-intensity ultrasound and microwave, alone or combined, promote Pd/C-catalyzed aryl–aryl couplings

Amination of benzylic C–H bonds by aryl azides catalysed by CoII(porphyrin) complexes. A new reaction leading to secondary amines and imines

Allylic Amination of Cyclohexene Catalyzed by Ruthenium Complexes. A New Reaction Involving an Intermolecular C−H Functionalization

Irradiation with light of wavelength higher than 350 nm of deaerated mixtures of nitrobenzene and cyclohexene leads to the reduction of the nitro-compound, with the formation of C 6 H 5 N(O)NC 6 H 5 (32%), C 6 H 5 NNC 6 H 5 (21%), C 6 H 5 NH 2 (15%), C 6 H 5 N(H)C 6 H 9 (32%). The same stable reduction products are obtained when the photochemical experiments are carried out in the presence of powder dispersions of TiO 2 or WO 3 or CdS. On the other hand, the photocatalytic contribution of these semiconductors plays an important role in the relative product distribution, which is observed to depend on both competitive adsorption–desorption equilibria of the involved reagents and intermediates on the solid surface and the different reducing power of the photoexcited semiconductors. Cyclohexene participates in the photoinduced reduction of nitrobenzene, undergoing oxidation, and producing the required electrons and protons. Experimental evidence for the formation of radical species deriving from the oxidation of this alkene is obtained by ESR spin trapping investigation. We report here for the first time, the photoinduced allylic amination of cyclohexene with nitrobenzene to give the important building block of synthetic interest C 6 H 5 N(H)C 6 H 9 .

Stefano Tollari

Papers

Amination of benzylic C-H bonds by arylazides catalyzed by CoII-porphyrin complexes: a synthetic and mechanistic study.

High-intensity ultrasound and microwave, alone or combined, promote Pd/C-catalyzed aryl–aryl couplings

Amination of benzylic C–H bonds by aryl azides catalysed by CoII(porphyrin) complexes. A new reaction leading to secondary amines and imines

Allylic Amination of Cyclohexene Catalyzed by Ruthenium Complexes. A New Reaction Involving an Intermolecular C−H Functionalization

Photochemical and photocatalytic reduction of nitrobenzene in the presence of cyclohexene