Although fire is now rarely used in synthetic chemistry, it was not until Robert Bunsen invented the burner in 1855 that the energy from this heat source could be applied to a reaction vessel in a focused manner. The Bunsen burner was later superseded by the isomantle, oil bath, or hot plate as a source for applying heat to a chemical reaction. In the past few years, heating and driving chemical reactions by microwave energy has been an increasingly popular theme in the scientific community. This nonclassical heating technique is slowly moving from a laboratory curiosity to an established technique that is heavily used in both academia and industry. The efficiency of "microwave flash heating" in dramatically reducing reaction times (from days and hours to minutes and seconds) is just one of the many advantages. This Review highlights recent applications of controlled microwave heating in modern organic synthesis, and discusses some of the underlying phenomena and issues involved.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.200400655

Controlled microwave heating in modern organic synthesis.

Since the discovery of organic azides by Peter Griess more than 140 years ago, numerous syntheses of these energy-rich molecules have been developed. In more recent times in particular, completely new perspectives have been developed for their use in peptide chemistry, combinatorial chemistry, and heterocyclic synthesis. Organic azides have assumed an important position at the interface between chemistry, biology, medicine, and materials science. In this Review, the fundamental characteristics of azide chemistry and current developments are presented. The focus will be placed on cycloadditions (Huisgen reaction), aza ylide chemistry, and the synthesis of heterocycles. Further reactions such as the aza-Wittig reaction, the Sundberg rearrangement, the Staudinger ligation, the Boyer and Boyer-Aube rearrangements, the Curtius rearrangement, the Schmidt rearrangement, and the Hemetsberger rearrangement bear witness to the versatility of modern azide chemistry.

Organic Azides: An Exploding Diversity of a Unique Class of Compounds

Asymmetric 1,3-Dipolar Cycloaddition Reactions

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.

Introduction Cationic domino reactions Anionic domino reactions Radical domino reactions Pericyclic domino reactions Photochemically induced domino processes Transition metal catalysis Domino reactions initiated by oxidation or reduction Enzymes in domino reactions Multicomponent reactions Special techniques in domino reactions

Domino Reactions in Organic Synthesis

Since 2013, Aust. J. Chem. has published an annual issue of invited papers showcasing the winners of awards, prizes, and medals from the Royal Australian Chemical Institute (RACI) and the Australian Academy of Science. In this November issue, we are pleased to publish 10 such papers from the 2016–2017 awardees. Mark Buntine (Curtin University), a past president of the RACI, was awarded the prestigious Leighton Memorial Medal. In a paper written with co-workers at Curtin, including Max Massi, the winner of the Organometallic Chemistry Award, the laser-based formation of copper nanoparticles (CuNPs) is described. The presence of N-donor ligands results in changes in the nanoparticle optical properties and particle size distributions, depending upon the nature of the donor ligands. The kinetics of formation of the CuNPs are found to be independent of the nature of the donor ligand. Joe Shapter (Flinders University) received the Fensham Medal for Outstanding Contribution to Chemical Education, and reports with co-workers at Flinders and Queensland University of Technology on applications of new hole transporting materials as the interlayer in graphene oxide/single-wall carbon nanotube heterojunctions, resulting in better performance of solar cells. W. Alexander Donald (UNSW), the recipient of the 2016 RACI Physical Chemistry Division Lectureship and the 2016 RACI Analytical and Environmental Chemistry Division Peter W. Alexander Medal, reports with colleagues at The University of Melbourne and Accurate Mass Scientific, Victoria, that the portable dielectric barrier discharge ionisation in a plasmabased ion source for mass spectrometry is significantly softer than in more widely-used plasma-based ionisation sources. This is important for the detection of intact molecules with thermolabile bonds, such as many explosives, and some chemical weapons and organic pollutants. Jason L. Dutton (La Trobe University) was the recipient of the Inorganic Division’s 2016 Alan Sargeson Lectureship. With M. Albayer, he describes reactions of classic iridium and rhodium complexes with iodine(III) oxidants, which result in two-electron oxidation. Ligand exchange and anion scrambling were observed in monodentate ligand-containing complexes, but I reagents reacted with chelating ligand-containing complexes without scrambling, so well-defined complexes could be isolated. Deanna D’Alessandro (The University of Sydney) is the recipient of the 2017 Australian Academy of Science Le Fèvre Memorial Prize as well as the Inorganic Division’s 2017 Alan Sargeson Lectureship. She reports on a coordination framework containing the novel photoactive azobenzene derivative, 5-((4-tert-butyl)phenylazo)isophthalic acid, which displays light-dependent spectroscopic properties. CarolHua, formerly a Ph.D. student at theUniversity of Sydney and now a post-doc at Northwestern University, USA, won the 2016 RACI Cornforth Award for the best Ph.D. thesis. The paper on redox-state dependent spectral properties of porous organic polymers containing furan, thiophene, and selenophene is based on her Ph.D. work with Deanna D’Alessandro. Redox-active porous organic polymers with heterocyclic linkers (furan, thiophene, and selenophene) were synthesised, and their electronic and spectral properties investigated as a function of redox state. Through the use of electron paramagnetic resonance (EPR) spectro-electrochemistry, it was found that the distinct redox states in these polymers could be accessed reversibly. Tom Davis (Monash University and University of Warwick, UK) was awarded the Polymer Division’s Batteard-Jordan Australian Polymer Medal for 2016. He reports on the synthesis of star polymers by RAFT polymerisation and their use as versatile nanoparticles with an emphasis on biomedical applications.

/pdf/celebrating-raci-and-academy-of-science-awards-2c2z1x594t.pdf

Curt Wentrup

Papers

Celebrating RACI and Academy of Science Awards

HCN Dimers: Photoelectron Spectrum of Iminoacetonitrile.