<?xml version="1.0" encoding="UTF-8" standalone="yes"?><oembed><version><![CDATA[1.0]]></version><provider_name><![CDATA[amphoteros]]></provider_name><provider_url><![CDATA[http://amphoteros.com]]></provider_url><author_name><![CDATA[ayudin2013]]></author_name><author_url><![CDATA[https://amphoteros.com/author/ayudin2013/]]></author_url><title><![CDATA[Isocyanides and Lewis acids (and a tribute to Paul&nbsp;Gassman)]]></title><type><![CDATA[link]]></type><html><![CDATA[<p>I really enjoyed reading Chris Vanderwal’s synthesis of kahalinol B published in <em>JACS</em> 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 &#8220;NC&#8221; functionality.</p>
<p><a href="https://amphoteros.files.wordpress.com/2015/05/441.jpg"><img data-attachment-id="3493" data-permalink="https://amphoteros.com/2015/05/07/isocyanides-and-lewis-acids-and-a-tribute-to-paul-gassman/44-5/" data-orig-file="https://amphoteros.files.wordpress.com/2015/05/441.jpg" data-orig-size="1004,489" data-comments-opened="1" data-image-meta="{&quot;aperture&quot;:&quot;0&quot;,&quot;credit&quot;:&quot;&quot;,&quot;camera&quot;:&quot;&quot;,&quot;caption&quot;:&quot;&quot;,&quot;created_timestamp&quot;:&quot;0&quot;,&quot;copyright&quot;:&quot;&quot;,&quot;focal_length&quot;:&quot;0&quot;,&quot;iso&quot;:&quot;0&quot;,&quot;shutter_speed&quot;:&quot;0&quot;,&quot;title&quot;:&quot;&quot;,&quot;orientation&quot;:&quot;0&quot;}" data-image-title="44" data-image-description="" data-medium-file="https://amphoteros.files.wordpress.com/2015/05/441.jpg?w=543&#038;h=275" data-large-file="https://amphoteros.files.wordpress.com/2015/05/441.jpg?w=1004" class="alignnone  wp-image-3493" src="https://amphoteros.files.wordpress.com/2015/05/441.jpg?w=543&#038;h=275" alt="44" width="543" height="275" /></a></p>
<p style="text-align:center;"><a href="http://pubs.acs.org/doi/abs/10.1021/jacs.5b01152">http://pubs.acs.org/doi/abs/10.1021/jacs.5b01152</a></p>
<p>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:</p>
<p style="text-align:center;"><a href="http://www.nature.com/nature/journal/v501/n7466/full/nature12472.html">http://www.nature.com/nature/journal/v501/n7466/full/nature12472.html</a></p>
<p>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 <em>cyanide</em> donor. That TMSCN can act as the <em>isocyanide</em> 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: “<em>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?”</em> 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 <em>JACS</em> back in 1982 (see the link below). As a matter of fact, he even had the well-known <em>OrgSyn</em> 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).</p>
<p style="text-align:center;"><a href="http://pubs.acs.org/doi/abs/10.1021/ja00385a078">http://pubs.acs.org/doi/abs/10.1021/ja00385a078</a></p>
<p style="text-align:center;"><a href="http://www.orgsyn.org/demo.aspx?prep=CV7P0294">http://www.orgsyn.org/demo.aspx?prep=CV7P0294</a></p>
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