Synthesis of (+)-Panamonon B, 7-epi-Panamonon B, and Their (Z)-Isomers

(+)-Panamonon B was synthesized with the key quaternary center (of a predefined absolute configuration) installed using Stoltz asymmetric allylation. The C-5 ketone functionality and the cross-conjugated enone moiety in the side chain were introduced via a photosensitized [2+4] cycloaddition of singlet oxygen to diene silyl enol ether and an aldol condensation under the conditions of Sugiura, respectively. The ¹H and ¹³C NMR of the synthetic and natural samples were fully consistent with each other. However, because two samples showed opposite signs for optical rotations, they must be antipodes to one another. The synthesis also provided valuable chances to observe unexpected, yet rather intriguing, phenomena such as a bulky substituent in an axial position of a cyclohexane ring and (E)-and (Z)-isomers with opposite signs for optical rotations despite their identical stereogenic centers. The rare occurrence of a bulky substituent in an axial position of a cyclohexane ring is rationalized as a consequence of the presence of a quaternary center and formation of the five-membered lactone fused to the six-membered ring, while the so far unnoticed influence of C═C geometry on optical rotation is shown to be consistent with the information encapsulated in several discrete pairs of similar compounds retrieved from the literature.