Paper of the Year (Part 2)

As I previously mentioned, the Glorius group has an annual paper of the year seminar (or two). As the first seminar is nearly upon us, and the wonderful @JessTheChemist over at The Organic Solution also yesterday called for nominations for paper of the year, I though time was ripe for posting our first nine.

It is worth bearing in mind that the Glorius groups’ primary research field is catalysis (transition metal and organocatalysis), and this is reflected in papers presented at our seminars.

So, in no particular order:

1) Selective C-H Fluorination of Pyridines and Diazines Inspired by a Classic Amination Reaction  (John F. Hartwig). This paper is just out, and as I knew it would be presented imminently I have not read it in detail, but a much sought after, safe, efficient, and broadly applicable fluorination of N-containing heterocycles seems to be the order of the day.

2) Amine(imine)diphosphine Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and Imines (Robert H. Morris). Another paper just out that I mentioned in passing last week. The role of hydrogenation in the preparation of organic molecules is unquestionable, and moving away from the typical heavy, expensive and toxic transitional metals is essential. Asymmetric iron catalysed hydrogenations are consequently one of the holy grails of this field.

3) Aerobic Dehydrogenation of Cyclohexanone to Phenol Catalyzed by Pd(TFA)2/2-Dimethylaminopyridine: Evidence for the Role of Pd Nanoparticles (Shannon S. Stahl). My paper of the year is this beautiful mechanistic study that demonstrates a two stage reaction, in which the first step is catalysed by a homogeneous Pd(II) species, and the second stage is catalysed by Pd nanoparticles generated from the Pd (II) precursor. A really magnificent study.

4) Water-Stabilized Three- and Four-Atom Palladium Clusters as Highly Active Catalytic Species in Ligand-Free C[BOND]C Cross-Coupling Reactions (Avelino Corma). A truly remarkable study delving into the black box of active catalytic species in Pd catalysis. It turns out 3-4 atom clusters of Pd are the business for traditional cross coupling reactions.

5) Enantio- and Diastereodivergent Dual Catalysis: α-Allylation of Branched Aldehydes (Erick M. Carreira). An elegant combination of metal and amine catalysis enables “fully stereo-divergent” access to all for stereoisomers of incredibly useful highly substituted  gamma,delta-unsatuarated aldehyde building blocks.

6) Organotextile Catalysis (Benjamin List). Our first metal free catalysis paper here! Here organocatalysts are supported for the first time on one of the most ubiquitous materials of our times, Nylon. Yes, you got it, essentially we have clothes that can do chemistry!

7) Enantioselective Photoredox Catalysis Enabled by Proton-Coupled Electron Transfer: Development of an Asymmetric Aza-Pinacol Cyclization (Robert R. Knowles) This is one I missed; the paper couples photoredox catalysis and chiral phosphoric acid catalysis.

8) Photoredox Activation for the Direct β-Arylation of Ketones and Aldehydes (David W. C. MacMillan) From the most prolific British chemist abroad? A step on from alpha-functionalisation using photoredox catalysis, and a product of design rather than serendipity as far as I know.

9) Complex N-Heterocycle Synthesis via Iron-Catalyzed, Direct C–H Bond Amination (Theodore A. Betley) Iron catalysed synthesis of saturated N-containing heterocycles. A really inspirational paper, and a tour de force in organometallic chemistry. I just wonder if an organic chemist could have got away without isolating any products?



Incase you were not sure about hydrogenation

If you were unsure about the significance of research into new hydrogenation catalysts here is some more food for thought.

3 papers published ‘back to back’ in Science:

Nanoscale Fe2O3-Based Catalysts for Selective Hydrogenation of Nitroarenes to Anilines (Beller)

Cobalt Precursors for High-Throughput Discovery of Base Metal Asymmetric Alkene Hydrogenation Catalysts (Chirik)

Amine(imine)diphosphine Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and Imines (Morris)

I won’t discuss the merits or otherwise of the papers, you can judge for yourselves, but this is indicative of the huge amount of research left to be done in this field and the significant impact it will continue to have for many, many years to come.