The outcome of pericyclic reactions con depend most simply on three conditions, any two of which determine the third. Whether the catalyst is Δ or hν (heat or light), the topology determining any stereochemistry and the participating electron count (4n+2/4n). It is always neat to conjure up a simple switch to toggle these; heat or light is simple, but what are the options for toggling the electron count?

The potential energy surface for a molecule tells us about how it might react. These surfaces have been charted for thousands of reactions using quantum mechanics, and their basic features are thought to be well understood. Coming across an entirely new feature is rare. So what do you make of the following? The reaction is shown above[cite]10.1039/P19920001709 [/cite], and on the face of it, it looks like a normal pericyclic cascade.

A game one can play with pericyclic reactions is to ask students to identify what type a given example is. So take for example the reaction below. The alternatives are: A cyclo-elimination reaction (red arrows). Two concurrent electrocyclic ring openings (blue and magenta arrows) Two consecutive electrocyclic ring openings Or could it be a hybrid with characteristics of both the first two?

As my previous post hints, I am performing my annual spring-clean of lecture notes on pericyclic reactions. Such reactions, and their stereochemistry, are described by a set of selection rules . I am always on the lookout for a simple example which can most concisely summarise these rules. The (hypothetical) one shown below I think nicely achieves this, and raises some interesting issues in the process.

When I first started giving lectures to students, it was the students themselves that acted as human photocopiers, faithfully trying to duplicate what I was embossing on the lecture theatre blackboard with chalk. How times have changed!

Not long ago, I described a cyclic carbene in which elevating the carbene lone pair into a π-system transformed it from a formally 4n-antiaromatic π-cycle into a 4n+2 aromatic π-cycle. From an entirely different area of chemistry, another example of this behaviour emerges; Schreiner’s[cite]10.1039/C2SC21555A[/cite] trapping and reactions of t-butyl-hydroxycarbene, as described on Steve Bachrach’s blog.

A reader asked me about the mechanism of the reaction of 2-picoline N-oxide with acetic anhydride to give 2-acetoxymethylpyridine (the Boekelheide Rearrangement[cite]10.1002/ejoc.201000936[/cite]). He wrote ” I don’t understand why the system should prefer to go via fragmentation-recombination (… the evidence being that oxygen labelling shows scrambling) when there is an easy concerted pathway available (… a

Sometimes the originators of seminal theories in chemistry write a personal and anecdotal account of their work. Niels Bohr[cite]10.1007/BF01326955[/cite] was one such and four decades later Robert Woodward wrote “ The conservation of orbital symmetry ” (Chem. Soc. Special Publications (Aromaticity), 1967 , 21 , 217-249;

It is always rewarding when one comes across a problem in chemistry that can be solved using a continuous stream of rules and logical inferences from them. The example below[cite]10.1039/P19930000299[/cite] is one I have been using as a tutor in organic chemistry for a few years now, and I share it here. It takes around 50 minutes to unravel with students.

If you search e.g. Scifinder for N,O-diphenyl hydroxylamine (RN 24928-98-1) there is just one literature citation, to a 1962 patent. Nothing else;