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

Spectroscopy is the study of matter interacting with electromagnetic radiation (e.g., light). The electromagnetic spectrum in Figure 1 illustrates the many different types of electromagnetic radiation, including gamma rays (γ-rays), X-rays, ultraviolet (UV) radiation, visible light, infrared (IR) radiation, microwaves, and radio waves. The frequency (ν) and wavelength (λ) ranges associated with each form of radiant energy are also indicated in Figure 1.

Introduction to Spectroscopy

In this critical review the applications of gold catalysed reactions in total synthesis during the years since our last article are reviewed. At the end of this article a literature analysis is conducted to evaluate the progress in this field.

Gold catalysis in total synthesis – recent achievements

GIAO NMR shift calculation has been applied to the challenging task of reliably assigning stereochemistry with quantifiable confidence when only one set of experimental data are available. We have compared several approaches for assigning a probability to each candidate structure and have tested the ability of these methods to distinguish up to 64 possible diastereoisomers of 117 different molecules, using NMR shifts obtained in rapid and computationally inexpensive single-point calculations on molecular mechanics geometries without time-consuming ab initio geometry optimization. We show that a probability analysis based on the errors in each 13C or 1H shift is significantly more successful at making correct assignments with high confidence than are probabilities based on the correlation coefficient and mean absolute error parameters. Our new probability measure, which we have termed DP4, complements the probabilities obtained from our previously developed CP3 parameter, which applies to the case of assig...

Assigning Stereochemistry to Single Diastereoisomers by GIAO NMR Calculation: The DP4 Probability

The Lycopodium alkaloids

Lycopodium alkaloids are unique heterocyclic alkaloids having C 11 N, C 15 N 2 , C 16 N, C 16 N 2 , C 22 N 2 , and C 27 N 3 types from genus Lycopodium and have attracted great interest from biogenetic and biological points of view as well as providing challenging targets for total synthesis This review covered the structure elucidation and biological activity of new Lycopodium alkaloids and total synthesis of some Lycopodium alkaloids reported in the literature from 2004 to July in 2008

The lycopodium alkaloids

Bioassay-guided purification from the seeds of Peganum harmala led to the isolation of harmine (1), harmaline (2), vasicinone (3), and deoxyvasicinone (4). Harmine (1) and harmaline (2) showed a moderate in vitro antiplasmodial activity against Plasmodium falciparum. Quinazoline alkaloid, vasicinone (3), showed a vasorelaxant activity against phenylephrine-induced contraction of isolated rat aorta.

Yusuke Hirasawa

Papers

The lycopodium alkaloids

Alkaloids from the seeds of Peganum harmala showing antiplasmodial and vasorelaxant activities

Cassiarins A and B, novel antiplasmodial alkaloids from Cassia siamea.

Lyconadin A, a Novel Alkaloid from Lycopodium complanatum

Sieboldine A, a novel tetracyclic alkaloid from Lycopodium sieboldii, inhibiting acetylcholinesterase.