Isocyanides and Lewis acids (and a tribute to Paul Gassman)

I really enjoyed reading Chris Vanderwal’s synthesis of kahalinol B published in JACS not too long ago. As someone who has had a keen interest in the chemistry of isocyanides, I have been attracted to the structure of kahalinol B and other natural products containing that venerable “NC” functionality.

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http://pubs.acs.org/doi/abs/10.1021/jacs.5b01152

In Chris’s synthesis, the key step that enables isocyanide group transfer (see the graphic above) involves some chemistry developed by Ryan Shenvi. That in itself was a notable advance:

http://www.nature.com/nature/journal/v501/n7466/full/nature12472.html

I am sure you all agree that these isocyanide transfer reactions represent very elegant ways to use TMSCN, which is typically known for its role as the cyanide donor. That TMSCN can act as the isocyanide source with alcohol and epoxide electrophiles is leading some students to suggest to me that this whole TMSCN/Lewis acid business might be a cool way to make novel isocyanides for multicomponent reactions. To that I say: “Sure, but let’s take a sober look. Why is it that no one feels any burning desire to cite Professor Paul Gassman’s contributions to this area?” I am not sure, maybe I am way off here, so you can be the judge about whether or not any of the recent isocyanide transfer reactions need to mention Paul’s name. Paul was a well-regarded scientist, by the way. He was the President of the ACS and, in his free time, published on the “isocyanide/smart Lewis choice” idea in JACS back in 1982 (see the link below). As a matter of fact, he even had the well-known OrgSyn prep dedicated to this chemistry (the last link below). You all know what that means: his epoxide ring opening reactions were no fluke. I think people need to acknowledge these seminal contributions for what they were, namely precedent-setting advances (which are important to cite).

http://pubs.acs.org/doi/abs/10.1021/ja00385a078

http://www.orgsyn.org/demo.aspx?prep=CV7P0294

One thought on “Isocyanides and Lewis acids (and a tribute to Paul Gassman)

  1. Pingback: Classics in Organic Chemistry, Part VII | musings on music and life

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