We were watching Goldfinger (1964) the other day. Again. You gotta love the real Bond movies. Anyways, in the opening scene, about 1 minute and 47 seconds into the movie, I was able to snap a frame with quite a lot of (medicinal) chemistry in it. The whole shot lasts for about two seconds and remains uncommented throughout the entire story, so I figured something had to be done about it. Here we go, 48 years later:

So, what have we got here? To the left in the background there are plants, which we can assume are cannabis sativa. To the right of them is a large table with what looks like bags of pills and stuff like that on it. Suspicious. In the foreground there are a bunch of dried poppies (opium, morphine, you know the drill). Finally, to the very right, three large distillation setups. Nice!

Another five seconds into the movie, after a pan to the left, barrels and barrels of nitromethane. Ha!

… which brings us closer to the article I spotted a couple of weeks ago and wanted to say something about, namely Org. Lett. 2012, ASAP (DOI: 10.1021/ol301713j)

The reasons I felt compelled to post a remark about this one were a) I love new cross-couplings, b) I love nitro-groups and not the least c) whenever you post something with nitro in the title, the big G blesses you with tons of extra traffic (freebie advice!).

To able to go directly from aromatic halides to alfa-nitrotoluenes, and then swiftly to the corresponding aldehydes, benzylamines, nitriles and so forth is pretty damn neat.

Read the paper and add this transformation to your arsenal. I am sure it will come handy one day.


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4 Responses to Goldfinger chemistry, nitromethane and cross-couplings

  1. James says:

    Great find! on both counts. I love nitro group chemistry too. You know what’s hard to find? A good review on nitrogen oxidation chemistry.

    • drfreddy says:

      True that. Probably because nitrogen oxidations almost never work. At least not in my hands. I have tried to go from amines to hydrxoylamines or hydrazines many times – and failed.

      One awesome transformation that I have had great success with, however, is going from benzophenone-oxime to the corresponding biphenylnitromethane, using sodium perborate in acetic acid. Reference: Synlett 1992, 337-339. (DOI: 10.1055/s-1992-22006) – curiously by Olah/ Prakash – names you have seen here before. Good stuff!

  2. JohnC says:

    This paper is a nice transformation especially because making the aryl nitromethanes was a pain in the ass before this. I was stuck with 45% yields of SM for a previous project, was def. not fun.

  3. milkshaken says:

    There is one lovely transformation: ArCH2NO2 -> in situ ArCNO (nitrile-N-oxide) for dipolar [3+2] addition (to acetylenes, olefins, enoleters etc). It uses NEt3 + PhNCO as a dehydrating agent and avoids redox chemistry (such as is the case of transforming ArCHO to ArCCl=NOH)

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