Wednesday, August 26, 2015

Giving Up Benzyne

From Rolf Huisgen's highly detailed and comprehensive biography The Adventure Playground of Mechanisms and Novel Reactions comes this rather eyebrow-lifting passage:
"I had several reasons for abandoning benzyne chemistry at the beginning of the 1960s. Many groups were active in the field, and other areas like 1,3-dipolar cycloaddition began to blossom in Munich. In addition, Georg Wittig, my venerated senior colleague, signaled in print and word that he regarded dehydrobenzene as his domain."

Left, benzyne, in one of its (many) accepted resonance forms
Right: Emeritus professor Rolf Huisgen, of dipolar cycloaddition fame

I wonder: Given the advances in benzyne chemistry over the past 112 years, and that up-and-coming groups make its study a central piece of their research portfolios, would this choice be made in today's research landscape? Readers, have you ever been asked to cease your studies in a certain area because someone more prestigious laid claim?

11 comments:

  1. My former research advisor told us a story about a strongly worded email he received from Katritzky in the vein of the "stay off my lawn" type of message

    ReplyDelete
  2. At the end of his paper on the discovery of the first persistent organic free radical (triphenylmethyl radical), Professor Moses Gomberg of the University of Michigan famously wrote, "This work will be continued and I wish to reserve the field for myself."

    ReplyDelete
  3. "Thus it appears to us that the possibility of synthesis of complex compounds related to or identical with natural products such as terpenes, sesquiterpenes, perhaps even alkaloids, has been moved to the near prospect. We explicitly reserve for ourselves the application of the reaction developed by us to the solution of such problems." – Diels and Alder, 1928

    ReplyDelete
    Replies
    1. That's a good one. "Developed by us", not one of Nature's most common reactions.

      Delete
  4. My PI commented once that he would stay away from natural products that fell into a category studied by a senior colleague. He made it clear, and I saw evidence several times later, that this was done out of respect on the part of my PI and not due to any pressure from the senior faculty member. I have, on the other hand, spoken to friends doing grad school at Princeton, who have commented that MacMillan views all things radical as his domain and feels the freedom to "adopt" any projects that junior colleagues might be working on. When people have picked the low-lying fruit, they start to fight over the scraps?

    ReplyDelete
    Replies
    1. Shotgun CollaborationAugust 26, 2015 6:09 PM

      Hah! Whoever you talked to has his/her head screwed on straight. Such was the genesis of a certain high-profile science paper: 1) associate professor's student (in collaboration with Merck, who got cut out of the final paper btw) gets initial hit, 2) senior professor hears about hit, despite not working with the metal that is the associate professor's specialty, 3) highly productive postdoc in senior professor's lab is put on the project, 4) senior professor tells associate professor, "we can either collaborate or compete; if we compete you will lose," leading to 'collaborative' paper, and 5) senior professor puts all of his lab on this new research area, effectively cutting the junior colleague out of what turned out to be a highly fruitful research topic (enough to sustain two prominent Ivy League labs).

      Delete
    2. In his book "An Introduction to Scientific Research," E. Bright Wilson described this thing as a "crude form of mental larceny."

      Delete
    3. SC, you forgot 6) field highly rewards senior professor for doing so. I'd say how disappointing it is that there are so many ruthless and amoral predators at the top of our field, but I think you can say that about nearly any line of work.

      While I'm at it, I'll commend the Associate Professor in this situation for quite effectively shutting up a lot of people who questioned her hire.

      Delete
  5. A.G. Perkin, Yorkshire College, 1897 - In J.Chem. Soc. vol 71, issue 1:

    "Luteolin - Since the publication of my last communication on this colouring matter, a paper has appeared by Herzig, which confirms those results excepting as regards a slight difference in the melting point of luteolin triethyl ether. He, however, mentions a second product formed during the ethylation of luteolin, although its nature and composition were not determined. Although no account of this substance appears in my paper, I was fully aware of its existence, but did not consider it necessary to mention it at the time, believing that the prior publication of my results was sufficient to reserve for me the further study of this reaction."

    ReplyDelete
  6. From an 1874 patent commentary, No. 105555:

    "If the patents of Grawitz for dyeing and printing afford a measure of his practical capacity, this patent throws a flood of light on his value as a theoretical chemist. We recommend its study to our fellow-chemists. One may be spared the detailed examination of all the experiments which have never been made, but only 'reserved'. The pretence of reserving all the metals and all the bases to submit them to this special reaction is very original. Why has not Grawitz reserved to himself for five years all the reactions of organic and mineral chemistry."

    ReplyDelete
  7. My boss is a pretty large name in organometallic chemistry with a large group. Once, during a group meeting, someone proposed a new methodology which was based off a young untenured professor's previous finding. He says, "Stop working on that right now. That's not what we do. Come up with something new. Our group has more funding and numbers than almost any other group. If I wanted to I could put 10 post-docs on this field and crush it before this guy published another paper. I'm not in that business. I'm in the business of finding new chemistry. Think harder." I was a first year when he said this. Made me proud of my advisor selection!

    ReplyDelete