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

Occurrence, Biogenesis, and Synthesis of Biologically Active Carbazole Alkaloids

https://chemistry.mdma.ch/hiveboard/rhodium/pdf/piper.phytochemistry.pdf

Phytochemistry of the genus Piper

Tubulin is the biochemical target for several clinically used anticancer drugs, including paclitaxel and the vinca alkaloids vincristine and vinblastine. This review describes both the natural and synthetic agents which are known to interact with tubulin. Syntheses of the more complex agents are referenced and the potential clinical use of the compounds is discussed. This review describes the biochemistry of tubulin, microtubules, and the mitotic spindle. The agents are discussed in relation to the type of binding site on the protein with which they interact. These are the colchicine, vinca alkaloid, rhizoxin/maytansine, and tubulin sulfhydryl binding sites. Also included are the agents which either bind at other sites or unknown sites on tubulin. The literature is reviewed up to October 1997. © 1998 John Wiley & Sons, Inc., Med Res Rev, 18, No. 4, 259–296, 1998.

Tubulin as a target for anticancer drugs: agents which interact with the mitotic spindle.

The recent advent of transition-metal mediated CH activation is revolutionizing the synthetic field and gradually infusing a “CH activation mind-set” in both students and practitioners of organic synthesis. As a powerful testament of this emerging synthetic tool, applications of CH activation in the context of total synthesis of complex natural products are beginning to blossom. Herein, recently completed total syntheses showcasing creative and ingenious incorporation of CH activation as a strategic manoeuver are compared with their “non-CH activation” counterparts, illuminating a new paradigm in strategic synthetic design.

C-H activation: a complementary tool in the total synthesis of complex natural products.

Novel Ring‐Opening Reaction of Chromanone Oxime.

Metal Reagents in Organic Reactions. Part 6. Reactions of Pyridine and Quinoline Derivatives with Mercury(II) and Thallium(III) Acetates.

A facile route to tetra-substituted pyrrolidines has been accomplished by 1,3-dipolar cycloaddition reaction. Several pyrrolidine compounds have significant biological activity. A highly electron-deficient dipolarophile, β-nitrostyrene, was reacted with nonstabilized azomethine ylides derived from aryl aldehyde and L-phenylglycine in dry dimethyl formanide. The structures and stereochemistry of the cycloadducts were established by infrared, NMR spectroscopy, and single-crystal x-ray crystallographic analyses.

One-Pot, Three-Component Cycloaddition of Nonstabilized Azomethine Ylides to β-Nitrostyrene, a Highly Electron Deficient Dipolarophile.

13 C NMR data for several 1-substituted prop-2-ynes and 1,4-bias derivatives of but-2-yne are reported with full assignments. Substituent effects of -X-aryl groups (X=O, S, NMe, SO 2 ) at the propargylic position on teh chemical shifts of the acetylenic carbons were determined

Carbon-13 NMR spectra of 1-substituted prop-2-ynes and 1,4-bis-derivatives of but-2-yne

Aromatic trifluoroacetyl derivatives on treatment with single electron transfer (SET) reagent, sodium naphthalenide, yield symmetrical defluorinated dimers, whereas for aliphatic trifluoroacetyl compounds the reaction usually fails. Investigations have been made for different substituents as well as for similar types of chloro and bromo compounds to establish the scope of the reaction.

Avijit Banerji

Papers

Novel Ring‐Opening Reaction of Chromanone Oxime.

Metal Reagents in Organic Reactions. Part 6. Reactions of Pyridine and Quinoline Derivatives with Mercury(II) and Thallium(III) Acetates.

One-Pot, Three-Component Cycloaddition of Nonstabilized Azomethine Ylides to β-Nitrostyrene, a Highly Electron Deficient Dipolarophile.

Carbon-13 NMR spectra of 1-substituted prop-2-ynes and 1,4-bis-derivatives of but-2-yne

Effect of Sodium Naphthalenide, a Key SET Reagent, on Trifluoroacetyl Derivatives.