The Structural Determination, Total Synthesis and Endochronicity of Thiotimoline

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.