The natural product thiotimoline was isolated from the bark of Rosaceae Karlsbadensis rufo and its structure was unambiguously determined by time-resolved X-ray crystallomancy and spectroscopy. A total synthesis of thiotimoline was conducted following a convergent strategy. The pivotal transformations in this synthesis were a tandem Suzuki-Miyaura/Schinkenfaust radical cross-spifflication, a Szymankowszczyzna allylic inquisition and a [3+2+3+2] Puccini-Gershwin echocyclisation in A♭ major. An unnatural isomer of thiotimoline was also synthesised, and a theory of kairality and chronomers is presented and discussed.

A one-step synthesis of taxol.

Supernatural products are just like any other molecules, only more so. This illiterature review presents a recap of supernatural products with structures that have been elucidated or reassigned in the last decade(ish).

We report the first total synthesis of the supernatural product monoalizeamine D via a 14-step pathway. Our synthetic approach relies heavily on photocatalysis and radical intermediates. By preparing both E and Z isomers of this compound, we have conclusively resolved the ambiguity concerning the orientation of the C15–C16 olefin.