The volumes ofAnnual Reports, Section Boffer a selective overview of advances in some aspects of organic chemistry, taken from the primary literature published over the previous year or two, with chapters written by experts in each field.This year, a number of recurring themes are evident in the various chapters, including organocatalysis and catalysis by gold. Indeed, both of these topics appear in Karl Hemming’s first contribution on heterocyclic chemistry, where other highlights include advances in new methods for the asymmetric epoxidation of α,β-unsaturated carbonyl species. Catalysis by noble metals also appears in Paul Davies’ Report on transition metals in organic synthesis, where another focus is on C–H activation and functionalization. Organocatalysis again this year has a chapter all to itself, by Ben Buckley, who comments on the enormous growth in this area over the last 10 years, and is also highlighted by Gareth Rowlands in his discussion of free-radical reactions, with a fascinating combination of photoredox chemistry with enamine catalysis.Other advances in synthetic methodology include new organic chemistry of silicon, phosphorus, sulfur, selenium, and tellurium, where Paul Taylor describes, among many other processes, the uses of organophosphorus and organosulfur species as coupling agents. Oxidation and reduction methods are covered for the first time by Simon Lewis, who has identified a number of significant new processes, for example site-selective epoxidation of polyprenols, bis(hydroxamic acid) ligands for vanadium(v)-catalysed enantioselective epoxidation, direct catalytic aziridination of styrenes with ammonia, adaptive supramolecular ‘METAMORPhos’ ligands for asymmetric alkene hydrogenation, and the use of ‘frustrated Lewis pairs’ to effect H2bond scission for imine and nitrile reduction. Steven Nolan and co-authors provide a further overview of the ever-growing interest in the use ofN-heterocyclic carbenes (NHCs), focusing on transition metal-mediated transformations.Biological catalysis in synthetic organic chemistry is again ably addressed by Gideon Grogan, who points to notable achievements including a carboxylesterase with specificity for tertiary alcohols that has been engineered for inverted enantioselectivity, a ketoreductase that has been used in combination with palladium catalysis to perform a two-step Suzuki-coupling/carbonyl reduction, and a coupling ofin silicoenzyme design with directed evolution techniques to deliver an enzyme which catalyses a reaction not known in Nature, the Kemp elimination, with far-reaching implications for the possible design of enzymatic catalysts in the future.Highlights of total syntheses of complex natural products are discussed by Yvette Jackson and Nadale Downer-Riley; their Report is organised according to the class of the natural products, and concentrates on the key strategic steps of each synthesis. Bob Hill focuses on marine natural products with unusual structures or interesting biological activities, and his chapter is organised by biogenetic origin, from polyketides, terpenoids, alkaloids and peptides; Scott Dalgarno, in his first contribution for Annual Reports, provides a commentary on significant developments in supramolecular chemistry under three headings covering molecular recognition, structure and assembly, and functional systems.Bioinspired organic chemistry is considered for the first time by Salvador Tomas, who describes in four sections a selection of contributions from researchers who, using organic chemistry tools and inspiration from biomolecular systems, have developed new techniques, approaches and applications. The first three sections deal with progress in organic chemistry inspired by the major classes of biomolecules. The fourth section focuses on recent developments in organic chemistry inspired by the complexity of biomolecular systems, and notes that ‘more than a decade after the first artificial self-replicators were described, a discipline that deals with complexity in artificial chemical systems is beginning to take shape, under the name of Systems Chemistry.’Stereochemistry and has long been integral to organic synthesis. But, the burgeoning number, and increasing complexity, of enantioselective processes has seen enantioselectivity develop into a research area of its own, particularly where catalysis is involved. Fundamental to understanding the often complex and esoteric influences in these reactions is the study of mechanism. We welcome a new author, Ai-Lan Lee, who reviews in detail some recent highlights. Her review concentrates on asymmetric Heck couplings, alkene metathesis and interlocked architectures. The subtle influences involved in Heck couplings are shown by a reaction where presence of an additional ‘spectator’ achiral ligand actually improves it by preventing catalyst precipitation. As for interlocked architectures a fascinating report of the ‘freezing’ of a dynamically racemising chiral rotaxane into uneven amounts ofRandSenantiomers is described.The mantle of covering reactivity in organised assemblies has been taken up by Niklaas Buurma and Lavinia Onel. They report papers covering “chameleon-type” behaviour of zwitterionic micelles, enzyme kinetics at the micellar interface, “DNA-based approaches to reactivity”, and a kinetic method for assessing antioxidant distribution between the various regions of an emulsion. Nanoparticle catalysis is also covered, including a report of a non-linear Arrhenius plot for hydrogenation by palladium nanoparticles within “hairy” silica.Developments in the field of computational organic chemistry continue apace. Steven Bachrach again provides a perceptive report, in which, for example, caution is urged in the use of composite methods. As last year, he has presented some intriguing papers. In one, the classic SN2 reaction is revealed in new complexity, while in another, a ‘tortuous’ inverted adamantane is presented!In NMR spectroscopy, Mark Edgar has written a report that helps the organic chemist make sense of this field in the face of the ever-rising tide of acronyms. Concentrating on the topics of speed and sensitivity, the solid-state, simulation and calculation, Mark shows how organic NMR spectroscopy has progressed far beyond the simple proton spectrum; an example is the ability of solid-state NMR to probe a35Cl counterion and to differentiate different polymorphs.Douglas Neckers has provided a comprehensive report ranging from ‘traditional’ photophysics, photochemistry and spectroscopy, through photochemistry related to DNA, to solar cells. Among the many articles reported is one describing a molecular folding screen that folds into a zigzag by photocycloaddition, and opens thermally. Another outlines the use of stilbene photoisomerisation to power a molecular muscle.The traditional three explicit mechanisms are again represented this year. In covering pericyclic reaction mechanisms, Dean Tantillo and Jeehiun Lee present many examples from the 2008 literature including retrocycloadditions of pyrollidinofullerenes, multidimensional tunnelling in 1,5-H shifts, and the lithium-catalysed Claisen rearrangement, to name but a few. Further examples are reported of bispericyclic reactions, these are reactions where the path bifurcates to alternative products after a single transition state. Polar mechanisms are reported by AnneMarie O’Donoghue and Chukwuemeka Isanbor. A phosphine-catalysed (3 + 2) cycloaddition of allene to alkeneviaa 1,3-dipole, but with several polar steps, and a study of the effect of metal ions on the hydrolysis of phosphate esters, are a couple of examples from many. Jim Tanko provides, as usual, an excellent report on radical mechanisms. The latest developments in substitution and atom transfer, addition/cyclisation, fragmentation and cascading rearrangement processes are considered. His report concludes with remarkable evidence that a flavin-tryptophane radical pair may provide the basis for a “chemical compass” used by birds for navigation.