I was looking at the synthesis of corallopyronin A in the following paper by Rentsch and Kalesse: Angew. Chem. Int. Ed. 2012, 51 (45), 11381–11384.

There is one reaction which is described as

oxidation and a retro Diels–Alder reaction generated pyrone

enter image description here

I understand that the DMP oxidises the secondary alcohol to a ketone, and at the end there is an intramolecular esterification to produce the lactone, but I don't quite understand how the retro Diels–Alder reaction works. Could someone explain the reaction steps?


Here is my assessment of the mechanism. You are correct about the Dess-Martin periodinane (DMP) oxidation of 1 to 2. The resulting ketone 2 can also exist as the enols (E)-3 and (Z)-4. Any one of the three can undergo a retro-Diels-Alder-like thermolysis, but I have chosen (Z)-4 for the convenience of cyclizing ketene 5, which has lost acetone in the thermolysis. Finally, the ketene 5 affords pyranone 6.

ADDENDUM: Citation for the "retro-Diels-Alder". A. R. Katritzky, Z. Wang, M. Wang, C. D. Hall and K. Suzuki, J. Org. Chem. 2005, 70, 4854. https://doi.org/10.1021/jo050307m


Your Answer

By clicking “Post Your Answer”, you agree to our terms of service, privacy policy and cookie policy

Not the answer you're looking for? Browse other questions tagged or ask your own question.