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Retraction Watch

Tracking retractions as a window into the scientific process

Chemistry journal and author retract paper dogged by questions since its publication in 2006

with 9 comments

A chemistry journal has retracted a 2006 paper that had knowledgeable researchers scratching their heads from the minute it was published.

Here’s the notice:

The following article from Angewandte Chemie International Edition, “Total Syntheses of Hexacyclinol, 5-epi-Hexacyclinol, and Desoxohexacyclinol Unveil an Antimalarial Prodrug Motif” by James J. La Clair, published online on February 9, 2006 in Wiley Online Library (http://onlinelibrary.wiley.com), has been retracted by agreement between the author, the journal Editor in Chief, Peter Gölitz, and Wiley-VCH Verlag GmbH & Co. KGaA. The retraction has been agreed due to lack of sufficient Supporting Information. In particular, the lack of experimental procedures and characterization data for the synthetic intermediates as well as copies of salient NMR spectra prevents validation of the synthetic claims. The author acknowledges this shortcoming and its potential impact on the community.

La Clair, of the Xenobe Research Institute, apparently presented the findings at the 231st American Cancer Society National Meeting in 2006.

The paper has been cited 11 times, according to CrossRef, as provided by Wiley.

Well-known blogger Derek Lowe has been writing about hexacyclinol since the paper appeared in 2006, and not in a flattering way:

The paper is remarkable in several ways, and not just because I’d never heard of La Clair. The synthesis is over 30 steps long, which is unfortunately not as uncommon as it should be. (I’m afraid that my bias against total synthesis is showing). But La Clair is the only author, which is highly unusual for such a large effort. And it must have been a large one, since the paper makes reference to starting on a molar scale and finished with over three grams of the penultimate intermediate. Experienced organic chemists will wonder if two or three decimal points have been misplaced there, but that’s what it says.

Lowe has much more, including what he calls a paragraph “for my fellow synthetic geeks.” He highlights one particular passage:

The strangest part of La Clair’s paper is its final footnote, added in proof. Here’s how it starts; make of this what you will: “The 1H NMR spectra for this Communication were determined by contract services. The spectra provided in the Supporting Information were collected by N. Voss (Berlin, Germany). The operator added the peak for CDCl3 to the spectrum of synthetic hexacyclinol (1), however, this was done incorrectly at 7.5 ppm and against the request of the author.” That doesn’t make a whole lot of sense. The NMR operator “added the peak” for solvent to a spectrum? Why? And he put the peak in at 7.5 ppm (the wrong place, for non-chemists)? With what, Photoshop? No, this is very strange indeed.

Lowe has posted a few more times on this case, including in 2009, about remaining questions.

We had a few questions ourselves — particularly why this retraction took six years. La Clair tells Retraction Watch:

This paper was retracted based on the fact that it lacked sufficient spectral data supporting the synthetic intermediates as well as detailed 2D NMR analyses on the isolated and synthetic final products; an omission that fueled considerable controversy. While many published synthetic and natural product isolation efforts can be found in the literature with similar lacks of data, the author elected to retract this paper due to the fact that this omission failed to meet the current expectations associated with the publication of total syntheses and natural product isolation. The author hopes that this incident inspires publishers, editors, reviewers and authors to advance more effective measures to check and require spectral data sets as a part of the publication process. In particular, there is currently a lack of tools for presenting raw data files along with publications.

Hat tip: Chemjobber, via Neil Withers and Stuart Cantrill

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Written by Ivan Oransky

November 14, 2012 at 3:45 pm

9 Responses

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  1. While it seems that there may be several things suspicious surrrounding this paper, the stated reason by the author, “this omission [of spectral data] failed to meet the current expectations associated with the publication of total syntheses…” is a bit concerning to me. Studies from six years ago can’t be expected to conform to “current expectations”, if those expectations are always changing (I’m not sure if this was the case in this example). We can’t go around retracting papers just because the standards have changed, or can we?

    Also, thought I’d share this from the Xenobe website: “XRI is a small non-profit research institute run by one individual, Dr. James La Clair. Its efforts have led to a modest series of publications and federally funded grants. To quell any potential rumors that may exist, Dr. La Clair does not take salary from this program nor does he use this program to lure in collaborators to take advantage of them.”

    significantfigures

    November 14, 2012 at 4:29 pm

    • lure in collaborators? that is indeed strange text.

      Noah

      November 16, 2012 at 2:28 pm

    • The expectations that are current have been the same for the last 30 years. There was no experimental data for all the intermediates in the paper and the only things were two NMR spectra of the final product and a derivative. It’s also impossible to do this work in one year working out of a Berlin warehouse with the help of a group of people called the ‘Bionic Brothers’ that were thanked in the acknowledgements and who the author later claimed he hired off the street and trained in organic synthesis.

      Anyways, the spectra provided are fabricated. When I looked at them originally six years ago, I noticed that they don’t have carbon 13 satellites when zoomed in (should be 0.5% the size of the main peak). Not all the fabricators forget to add in this feature, but a surprising number of organic chemists forget about these peaks. The main peaks were obviously put in there by some NMR prediction software which doesn’t add the carbon 13 satellites. The paper should have been retracted for fraud, it was a clear case for me after looking at the fake spectra for a few minutes.

      blatnoi

      November 16, 2012 at 6:25 pm

    • “nor does he use this program to lure in collaborators to take advantage of them”
      The kind of out of the blue denial that makes you think that this is exactly what is going on!

      Jennifer Lynch

      November 17, 2012 at 5:12 am

  2. Not a moment too soon. Both the Angewandte editor and La Clair are beating about the bush here. I particularly like La Clair’s reflective tone on his hopes that “this incident inspires publishers, editors, reviewers and authors to advance more effective measures to check and require spectral data sets as a part of the publication process.”. Yeah, right. But I think that the most important job for the editors and reviewers is to weed out fraudsters. Of course checking the provided NMR spectra is also important. Especially, if they look computer generated and the author claims to have lost all the pertinent raw FIDs.
    In this particular case, La Clair never even made hexacyclinol because the structure of this natural product was revised AFTER La Clair had published his paper. So, La Clair’s paper describes “the synthesis” of a wrong compound. Yet, its NMR spectra (both 13C and 1H) are identical with the spectra of haxacyclinol. One cannot help but smile.

    chirality

    November 14, 2012 at 8:00 pm

  3. Significant Figures: the standards of characterization of organic compounds, such as those relevant for this manuscript, have not changed significantly. The goalposts have not moved.

    It is disappointing that Angewandte doesn’t call a spade a spade: La Clair almost certainly fabricated the entire paper – so blatantly that the reviewers should have caught it. He has had ample opportunity to come clean, but instead he issues a statement about poor characterization and the benefit to the community for lessons learned.

    Why doesn’t the journal come out and say “The paper has been retracted because of strong evidence of fabrication and an inability of the author to provide convincing evidence that the reported experiments were performed.”?

    Special Guest Lecturer

    November 15, 2012 at 5:09 pm

    • Simple.
      Such a blatant fraud was not caught by the reviewers, all of them, and the journal is trying its best to shield that fact.

      (CH3)2N-

      December 31, 2012 at 12:47 pm

    • Totally agree. There is no other conclusion possible: this paper was fabricated in its entirety.

      On the other hand, not so long ago another group of reviewers failed to ask pertinent questions on a paper claiming the oxidation of alcohols catalysed by sodium hydride. No matter how little time or availability you may have to review a paper, letting anything of the caliber of these two blusters get through is rather embarrassing to the profession.

      Petinga

      January 28, 2013 at 1:11 am

  4. What is sad is that this paper has actually been dedicated to the memory of a fellow chemist U. Graffe!

    Gurunath Ramathanan

    November 19, 2012 at 3:50 am


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