Stereochemical Reassignment of Mehta and Kundu’s Spiculoic Acid A Analogue
Balwin, Kirkham and Lee. Org. Lett., 2006, ASAP. DOI: 10.1021/ol062361a.
Mehta and Kundu. Org. Lett., 2005, 7, 5569 – 5572. DOI: 10.1021/ol0521329.
Now this is a little scary. Both Sir Jack Baldwin’s group at Oxford and Mehta’s group at the Indian Institute of Science were working on the total synthesis of Spiculoic Acid A. Kundu published the Org. Lett. referenced above, last year, showing their progress towards the target, but it’s taken until now for someone to spot the problems with the paper. Baldwin’s group read the paper thoroughly as part of their publication preparation, and found quite a few problems.
Amazingly, Kundu assigned the stereochemistry quite incorrectly, originating from a Sharpless epoxidation where they predicted the wrong outcome… this in turn led to the incorrect configuration at many of the stereocenters. To compound this, stereocenters invert in configuration during the synthetic scheme for no apparent reason, and the nOe-NMR data looks distinctly suspect.
Come on ACS, lets referee papers properly!
Also, loads more on this over at Curly Arrows… and I should thank the person who emailed me about this (I won’t mention names as some people like to remain anonymous).