The direct functionalization of C-H bonds in organic compounds has recently emerged as a powerful and ideal method for the formation of carbon-carbon and carbon-heteroatom bonds. This Review provides an overview of C-H bond functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets.

C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals

The Diels-Alder reaction has both enabled and shaped the art and science of total synthesis over the last few decades to an extent which, arguably, has yet to be eclipsed by any other transformation in the current synthetic repertoire. With myriad applications of this magnificent pericyclic reaction, often as a crucial element in elegant and programmed cascade sequences facilitating complex molecule construction, the Diels-Alder cycloaddition has afforded numerous and unparalleled solutions to a diverse range of synthetic puzzles provided by nature in the form of natural products. In celebration of the 100th anniversary of Alder's birth, selected examples of the awesome power of the reaction he helped to discover are discussed in this review in the context of total synthesis to illustrate its overall versatility and underscore its vast potential which has yet to be fully realized.

https://www.ch.ic.ac.uk/local/organic/pericyclic/DA.pdf

The Diels--Alder reaction in total synthesis.

Metal-catalysed C–H bond functionalisation has had a significant impact on how chemists make molecules. Translating the methodological developments to their use in the assembly of complex natural products is an important challenge for the continued advancement of chemical synthesis. In this tutorial review, we describe selected recent examples of how the metal-catalysed C–H bond functionalisation has been able to positively affect the synthesis of natural products.

Recent developments in natural product synthesis using metal-catalysed C–H bond functionalisation

The palladium-catalyzed α-arylation of ketones has become a useful and general synthetic method. In this process, an enolate is generated from a ketone and base in the presence of an aryl halide, and a palladium catalyst couples this enolate with the aryl halide. With the advent of new catalysts composed of sterically hindered, electron-rich alkylphosphine and N-heterocyclic carbene ligands, this process now encompasses a broad range of enolates and related anions, including those derived from amides, esters, aldehydes, nitriles, malonates, cyanoesters, nitroalkanes, sulfones, and lactones. In the proposed mechanism for this reaction, the carbon−carbon bond of the product is formed by reductive elimination from an arylpalladium enolate intermediate. The structures and reactions of arylpalladium complexes of enolate, cyanoalkyl, and malonate ions have been studied to determine how the binding mode and electronic and steric parameters influence the rate and mechanism of reductive elimination.

Palladium-Catalyzed α-Arylation of Carbonyl Compounds and Nitriles

Die direkte Funktionalisierung von C-H-Bindungen in organischen Molekulen hat sich in jungster Zeit zu einer wirksamen und idealen Methode entwickelt, mit der Kohlenstoff-Kohlenstoff- und Kohlenstoff-Heteroatom-Bindungen geknupft werden konnen. Der Aufsatz gibt einen Uberblick uber die Strategien, die durch Funktionalisierung von C-H-Bindungen eine rasche Synthese von biologisch aktiven Verbindungen wie Naturstoffen und pharmazeutischen Zielsubstanzen ermoglichen.

Funktionalisierung von C‐H‐Bindungen: neue Synthesemethoden für Naturstoffe und Pharmazeutika

Synthetic studies on tetrodotoxin and related compounds. IV. Stereospecific total syntheses of DL-tetrodotoxin

Synthetic studies on tetrodotoxin and related compounds. III. Stereospecific synthesis of an equivalent of acetylated tetrodamine

Synthetic studies toward mitomycins. 2. Total synthesis of dl-porfiromycin

Rossi and J. F. Bunnett, ibid., 38, 3020 (1973); (c) J. V. Hay, T. Hudlicky, and J. F. Wolfe, J. Am. Chem. Soc., 97, 374 (1975): (d) M. F. Semmelhack, B. P. Chong, R. D. Stauffer, T. D. Rogerson, A. Chong, and L. D. Jones, ibid., 97, 2507 (1975). (3) The 'H NMR spectra of 3 and 4 are consistent with the assigned stereochemistry: 3 (CCI4, TMS), 6 7.1 (br s, 5 H), 6.3 (d, J = 12, 1 H), 5.5 (d, J =

Synthetic studies toward mitomycins. 1. Total synthesis of deiminomitomycin A.

Synthetic approach towards tetrodotoxin. II. A stereospecific synthesis of a compound having the same six chiral centers on the cyclohexane ring as those of tetrodotoxin

F. Nakatsubo

Papers

Synthetic studies on tetrodotoxin and related compounds. IV. Stereospecific total syntheses of DL-tetrodotoxin

Synthetic studies on tetrodotoxin and related compounds. III. Stereospecific synthesis of an equivalent of acetylated tetrodamine

Synthetic studies toward mitomycins. 2. Total synthesis of dl-porfiromycin

Synthetic studies toward mitomycins. 1. Total synthesis of deiminomitomycin A.

Synthetic approach towards tetrodotoxin. II. A stereospecific synthesis of a compound having the same six chiral centers on the cyclohexane ring as those of tetrodotoxin