Iron Catalysis in Organic Synthesis

The coupling of aryl or vinyl halides with terminal acetylenes catalysed by palladium and other transition metals, commonly termed as Sonogashira cross-coupling reaction, is one of the most important and widely used sp2–sp carbon–carbon bond formation reactions in organic synthesis, frequently employed in the synthesis of natural products, biologically active molecules, heterocycles, molecular electronics, dendrimers and conjugated polymers or nanostructures. This critical review focuses on developments in the Sonogashira reaction achieved in recent years concerning catalysts, reaction conditions and substrates (352 references).

Recent advances in Sonogashira reactions

Chemistries that Facilitate Nanotechnology Kim E. Sapsford,† W. Russ Algar, Lorenzo Berti, Kelly Boeneman Gemmill,‡ Brendan J. Casey,† Eunkeu Oh, Michael H. Stewart, and Igor L. Medintz*,‡ †Division of Biology, Department of Chemistry and Materials Science, Office of Science and Engineering Laboratories, U.S. Food and Drug Administration, Silver Spring, Maryland 20993, United States ‡Center for Bio/Molecular Science and Engineering Code 6900 and Division of Optical Sciences Code 5611, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States College of Science, George Mason University, 4400 University Drive, Fairfax, Virginia 22030, United States Department of Biochemistry and Molecular Medicine, University of California, Davis, School of Medicine, Sacramento, California 95817, United States Sotera Defense Solutions, Crofton, Maryland 21114, United States

Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology.

Over the past 40 years, transition metal catalysis has enabled bond formation between aryl and olefinic (sp(2)) carbons in a selective and predictable manner with high functional group tolerance. Couplings involving alkyl (sp(3)) carbons have proven more challenging. Here, we demonstrate that the synergistic combination of photoredox catalysis and nickel catalysis provides an alternative cross-coupling paradigm, in which simple and readily available organic molecules can be systematically used as coupling partners. By using this photoredox-metal catalysis approach, we have achieved a direct decarboxylative sp(3)-sp(2) cross-coupling of amino acids, as well as α-O- or phenyl-substituted carboxylic acids, with aryl halides. Moreover, this mode of catalysis can be applied to direct cross-coupling of C(sp³)-H in dimethylaniline with aryl halides via C-H functionalization.

/pdf/merging-photoredox-with-nickel-catalysis-coupling-of-a-200ydcysj9.pdf

Merging photoredox with nickel catalysis: Coupling of α-carboxyl sp3-carbons with aryl halides

Conventional oxidations of organic compounds formally transfer hydrogen atoms from the substrate to an acceptor molecule such as oxygen, a metal oxide, or a sacrificial olefin. In acceptorless dehydrogenation (AD) reactions, catalytic scission of C-H, N-H, and/or O-H bonds liberates hydrogen gas with no need for a stoichiometric oxidant, thereby providing efficient, nonpolluting activation of substrates. In addition, the hydrogen gas is valuable in itself as a high-energy, clean fuel. Here, we review AD reactions selectively catalyzed by transition metal complexes, as well as related transformations that rely on intermediates derived from reversible dehydrogenation. We delineate the methodologies evolving from this recent concept and highlight the effect of these reactions on chemical synthesis.

http://science.sciencemag.org/content/sci/341/6143/1229712.full.pdf

Applications of acceptorless dehydrogenation and related transformations in chemical synthesis.

Phosphine-Free Well-Defined Mn(I) Complex-Catalyzed Synthesis of Amine, Imine, and 2,3-Dihydro-1H-perimidine via Hydrogen Autotransfer or Acceptorless Dehydrogenative Coupling of Amine and Alcohol

The synthesis of terminal, as well as internal, olefins was achieved by the one-step olefination of alcohols with sulfones catalyzed by a ruthenium pincer complex. Furthermore, performing the reaction with dimethyl sulfone under mild hydrogen pressure provides a direct route for the replacement of alcohol hydroxy groups by methyl groups in one step.

Direct catalytic olefination of alcohols with sulfones.

Efficient and selective direct synthesis of secondary amines from primary alcohols and ammonia with liberation of water has been achieved, with high turnover numbers and with no generation of waste. In case of benzylic alcohols, imines rather than amines are obtained. This atom economical, environmentally benign reaction is homogenously catalyzed by a well-defined bipyridine based Ru(II)-PNN pincer complex.

https://link.springer.com/content/pdf/10.1007%2Fs10562-014-1422-2.pdf

Dipankar Srimani

Papers

Phosphine-Free Well-Defined Mn(I) Complex-Catalyzed Synthesis of Amine, Imine, and 2,3-Dihydro-1H-perimidine via Hydrogen Autotransfer or Acceptorless Dehydrogenative Coupling of Amine and Alcohol

Direct catalytic olefination of alcohols with sulfones.

Direct Synthesis of Secondary Amines From Alcohols and Ammonia Catalyzed by a Ruthenium Pincer Complex

Palladium nanoparticle catalysis: borylation of aryl and benzyl halides and one-pot biaryl synthesis via sequential borylation-Suzuki–Miyaura coupling

Ruthenium Pincer Complex Catalyzed Selective Synthesis of C‐3 Alkylated Indoles and Bisindolylmethanes Directly from Indoles and Alcohols