“Black Swan Events” in Organic Synthesis

William Nugent
Angew. Chem. Int. Ed.
DOI: 10.1002/anie.201202348

The moral of this article can be summarised in three words of folk wisdom: never say never. This article provides a refreshing insight into the misplaced preconceptions of chemists working in previous decades, and how these preconceptions were overturned.

The author lays out a series of dogmatic statements which over the past two decades have been proven incorrect. These statements are classed into two categories depending whether they were brought down by a single publication – “Change through revolution”, or a series of reports – “Change through evolution”.

A selected few are:

“Gold compounds are simply to unreactive to be useful as homogeneous catalysts”

A report by Teles et al. in 1998 demonstrated that a cationic Au(I) complex catalyses the addition of oxygen nucleophiles to acetylenes:

“Olefin metathesis is an ill-defined reaction of olefinic hydrocarbons and unlikely to find any use in organic synthesis”

For students studying organic synthesis today, it’s hard to imagine a time before ubiquitous olefin metathesis, more so that it was considered so far out of reach. R.H. Grubbs ultimately shared the Nobel Prize in Chemistry in 2005 for his research on ruthenium catalysed olefin metathesis.

“Efficient enantioselective catalysis requires the use of a metal complex”

And then came one of the most elegant and sophisticated aspects of catalysis in organic synthesis: organocatalysis, with the work of MacMillan, List, Barbas and others.

As the author points out, a common characteristic of the above overruled statements is that often, the scientific literature contained hints that the “common belief” was incorrect. However, these hints were not picked up on until a report was published proving that the original discounted phenomenon was in fact achievable.

The discovery of something completely new and revolutionary is often preceded by flashes of insights or moments of wisdom that will most probably be ignored until three or four decades later when someone has the curiosity to move it forwards.

So what assumptions about the behavior of molecules do we make today that will populate a surrogate of this article in 50 years?


One thought on ““Black Swan Events” in Organic Synthesis

  1. mamid

    Replace the capital h with a small one in the straight brackets in the first figure/reaction. I think Richard Schrock is also worth mentioning, since he produced the first well-defined efficient metathesis catalyst(s). True, Grubbs’s are more robust and therefore more widely employed (by a huge margin, actually).


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