3.7. Palladium Nanoparticles as Catalysts 888 3.8. Other Transition-Metal Complexes 888 3.9. Transition-Metal-Free Reactions 889 4. Applications 889 4.1. Alkynylation of Arenes 889 4.2. Alkynylation of Heterocycles 891 4.3. Synthesis of Enynes and Enediynes 894 4.4. Synthesis of Ynones 896 4.5. Synthesis of Carbocyclic Systems 897 4.6. Synthesis of Heterocyclic Systems 898 4.7. Synthesis of Natural Products 903 4.8. Synthesis of Electronic and Electrooptical Molecules 906

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Chem.%20Rev/Chem.%20Rev.%202007,%20107,%20874-922.pdf

The Sonogashira Reaction: A Booming Methodology in Synthetic Organic Chemistry†

The substituted indole nucleus [indole is the acronym from indigo (the natural dye) and oleum (used for the isolation)] is a structural component of a vast number of biologically active natural and unnatural compounds. The synthesis and functionalization of indoles has been the object of research for over 100 years, and a variety of well-established classical methods are now available, to name a few of them, the Fisher indole synthesis, the Gassman synthesis of indoles from N-halo-anilines, the Madelung cyclization of N-acyl-o-toluidines, the Bischler indole synthesis, the Batcho-Leimgruber synthesis of indoles from o-nitrotoluenes and dimethylformamide acetals, and the reductive cyclization of o-nitrobenzyl ketones.1 In the last 40 years or so, however, palladiumcatalyzed reactions, generally tolerant of a wide range of functionalities and therefore applicable to complex molecules, have achieved an important place in the arsenal of the practicing organic chemist. Since the invention of an industrial process for the palladium-catalyzed production of acetaldehyde from ethylene in the presence of PdCl2 and CuCl2, an everincreasing number of organic transformations have been based on palladium catalysis. Almost every area of the organic synthesis has been deeply influenced by the profound potential of this versatile transition metal, modifying the way organic chemists design and realize synthetic processes.2,3 Because of its catalytic nature, palladium-catalyzed synthesis can provide access to fine chemicals, agrochemical and pharmaceutical intermediates, and active ingredients in fewer steps and with less waste than classical † In memory of Prof. Bianca Rosa Pietroni, a colleague and very close friend. * To whom correspondence should be addressed. Phone: + 39 (06) 4991-2785. Fax: + 30 (06) 4991-2780. E-mail: sandro.cacchi@ uniroma1.it. 2873 Chem. Rev. 2005, 105, 2873−2920

Synthesis and functionalization of indoles through palladium-catalyzed reactions

Transition-metal-catalyzed addition of heteroatom-hydrogen bonds to alkynes.

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/Heck-Larock%202006.pdf

Synthesis of heterocycles via palladium-catalyzed oxidative addition.

https://chemistry.mdma.ch/hiveboard/rhodium/pdf/indole.synth.review.1994-99.pdf

Recent developments in indole ring synthesis—methodology and applications

The reaction of N-(2-bromophenyl)-and N-(2-iodophenyl)methanesulfonamide with terminal acetylenes in the presence of dichlorobis(triphenylphosphine)palladium yielded 1-methylsulfonyl-indoles having carbon-functional groups at the 2-position, such as hydroxmethyl, 2-hydroxyethyl, diethoxymethyl, 2-ethoxycarbonylethyl, etc., in one step.

Condensed Heteroaromatic Ring Systems. XIII. : One-Step Synthesis of 2-Substituted 1-Methylsulfonylindoles from N-(2-Halophenyl)methanesulfonamides

Palladium-catalyzed cyclization of β-(2-halophenyl)amino substituted α,β-unsaturated ketones and esters, prepared from 2-haloanilines by three different methods, gave 2,3-disubstituted indoles.

Condensed Heteroaromatic Ring Systems; XVII:1 Palladium-Catalyzed Cyclization of β-(2-Halophenyl)amino Substituted α,β-Unsaturated Ketones and Esters to 2,3-Disubstituted Indoles

The palladium-catalyzed coupling reaction of 3-iodoindoles possessing an electron-withdrawing group at the 1- or 2-position with terminal acetylenes smoothly proceeded to yield 3-ethynylindoles. Similarly, the reaction of 3-iodobenzo[b]thiophene gave the expected products, but the reaction of 3-bromobenzo[b]furan provided resinous materials.

Tatsuo Nagano

Papers

Condensed Heteroaromatic Ring Systems. XIII. : One-Step Synthesis of 2-Substituted 1-Methylsulfonylindoles from N-(2-Halophenyl)methanesulfonamides

Condensed Heteroaromatic Ring Systems; XVII:1 Palladium-Catalyzed Cyclization of β-(2-Halophenyl)amino Substituted α,β-Unsaturated Ketones and Esters to 2,3-Disubstituted Indoles

Palladium-Catalyzed Coupling Reaction of 3-Iodoindoles and 3-Iodobenzo[b]thiophene with Terminal Acetylenes