Imagine that your name was Smith, and you had synthesized a molecule named Interestingolide. Now, if someone published a paper with the title "Reassignment of the Structure of Smith's Interestingolide", how would you feel? Well, that's what has happened to 'Mehta and Kundu's Spiculoic Acid' whose published structure has been refuted by Oxford's Jack Baldwin. What is interesting is that the original group seems to have incorrectly predicted the stereochemistry of the product of a Sharpless epoxidation. The substrate is simple, so is the product, and it should not have been difficult to use Sharpless's mnemonic device to do this prediction. As is clear from the diagram below, the Sharpless mnemonic device makes it clear that holding the allylic alcohol in the orientation shown and using D (-) DET, you should get the alpha epoxide.
The rest of Baldwin's analysis follows, but this initial incorrect prediction sets the stage for all that. Maybe the grad student did the stereochemical prediction, and the professor either trusted him, or did not look closely enough at his analysis. Well, better luck next time, and I will stop speculating.
* Incorrect prediction:
* Correct prediction:
* Sharpless mnemonic device:
Org. Lett.; (Letter); 2006; ASAP Article; DOI: 10.1021/ol062361a
14 hours ago in Pleiotropy