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.

 

Support Synthetic Remarks

You know it is the right thing to do

Bitcoin  (BTC)  12KejdK6zwYhPr1S6JB1d3khGCPAbsUDMA
Litecoin (LTC)  LdK1zKCGJcovPogME7QRkTpk2zThN9aHcK
Ethereum (ETH)  0x7095c468393C31B705Ad2fA79a6cf87E90E2d823
Ripple   (XRP)  rfUfHjTUcRoCcuiaMTb9PVZAJu76YzaHmb


—DrFreddy

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)

Leave a Reply

Your email address will not be published. Required fields are marked *