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DBL%20Hendrix%20small.png College chemistry, 1983

Derek Lowe The 2002 Model

Dbl%20new%20portrait%20B%26W.png After 10 years of blogging. . .

Derek Lowe, an Arkansan by birth, got his BA from Hendrix College and his PhD in organic chemistry from Duke before spending time in Germany on a Humboldt Fellowship on his post-doc. He's worked for several major pharmaceutical companies since 1989 on drug discovery projects against schizophrenia, Alzheimer's, diabetes, osteoporosis and other diseases. To contact Derek email him directly: Twitter: Dereklowe

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May 23, 2013

Alkynes and Nitriles

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Posted by Derek

Put this one in the category of "reactions you probably wouldn't have thought of". There's a new paper in Organic Letters on cleaving a carbon-carbon triple bond, yielding the two halves as their own separate nitriles.
It seems to be a reasonable reaction, and someone may well find a use for it. I just enjoyed it because it was totally outside the way that I think about breaking and forming bonds. And it makes me wonder about the reverse: will someone find a way to take two nitriles and turn them into a linked alkyne? Formally, that gives off nitrogen, so you'd think that there would be some way to make it happen. . .

Comments (10) + TrackBacks (0) | Category: Chemical News


1. Colorblind Chemist on May 23, 2013 12:40 PM writes...

Well, you can do alkyne metathesis with an alkyne and a nitrile to yield the corresponding crossed alkyne and nitrile, so I suppose it wouldn't be impossible to get two nitriles to cross yielding N2 and an alkyne, but then of course that would be a substrate (likely a better one) for the reaction...

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2. Hap on May 23, 2013 12:49 PM writes...

Could you bias the catalyst sterically so that it couldn't bind two alkynes or an alkyne and a nitrile but only two nitriles? (perhaps by formation of a metal-C complex with hindrance so that only an N could point toward the metal center and the nitrile substituents would have to be next to each other)

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3. ROGI on May 23, 2013 3:24 PM writes...

The (very) limiting aspect of this reaction is that both ends of the acetylene needs to be substituted with aryl groups, giving one cyanobenzene derivatives. Still, a nice paradigm shifter to think more deeply about the mechanism.

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4. Yancey Ward on May 23, 2013 5:59 PM writes...

I tried to think of a reason I would want to use this to make a nitrile, and I can't think of one.

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5. Anonymous on May 23, 2013 8:27 PM writes...

De-Click Chemistry;)

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6. milkshake on May 23, 2013 9:28 PM writes...

I hope that no-one is going to use this, generating iodazide IN3, even in situ, 2.4 equiv per acetylene substrate, then performing thermolysis on the bis-adduct - is not charming.

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7. Jim on May 24, 2013 9:18 AM writes...

@ 5 - perhaps it could be called "snap" chemistry

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8. David on May 24, 2013 10:38 AM writes...

Exactly. That's what I was thinking

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9. newnickname on May 28, 2013 3:06 PM writes...

@4, a reason: A masked (protected) nitrile in synthesis. Carry through your aryl nitrile ArCN as ArCCAr (or Ar'), and unmask it at the end. Unsym (Ar .dne. Ar'), it's wasteful with poor atom economy. If symmetrical, ArCCAr --> 2 ArCN is a very "reflexive" (Bertz) and efficient synthesis.

If your Rosenmund ArBr -Cu-> ArCN Reaction doesn't work, do a Sonogashira coupling followed by Yanada splitting.

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10. anon on June 5, 2013 3:24 PM writes...

Similar alkyne cleavage chemistry with TMSN3 and Ag catalysis (no NIS or likely IN3 intermediate) came out in ACIE a few weeks prior.


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