Total Synthesis of Racemic Thieno[3,2-f]thiochromene Tricarboxylate, a Luciferin from Marine Polychaeta Odontosyllis undecimdonta

Abstract

We report the first total synthesis of racemic Odontosyllis undecimdonta luciferin, a thieno­[3,2-f]­thiochromene tricarboxylate comprising a 6-6-5-fused tricyclic skeleton with three sulfur atoms in different electronic states. The key transformation is based on tandem condensation of bifunctional thiol-phosphonate, obtained from dimethyl acetylene dicarboxylate, with benzothiophene-6,7-quinone. The presented convergent approach provides the synthesis of the target compound with a previously unreported fused heterocyclic core in 11 steps, thus allowing for unambiguous confirmation of the chemical structure of Odontosyllis luciferin by 2D-NMR spectroscopy.

Bioluminescence of (R)-Cypridina Luciferin with Cypridina Luciferase

“…This result is reasonable based on the fact that the reaction of CypLase with the CypL analog that had a propyl moiety substituted for the original chiral sec -butyl moiety at the C2 position of the imidazopyrazinone ring gave 67% of the original light yield, suggesting that the recognition of the sec -butyl moiety in CypLase for the luminescence reaction is not especially strict. It is noted that some known luciferins including CypL are chiral compounds, and their chirality is recognized by their corresponding luciferases for the luminescence reaction [ 37 , 38 , 39 , 40 ]. For example, in the firefly bioluminescence system, D-firefly luciferin is the substrate for firefly luciferase, whereas the ( R )-enantiomer ( l -firefly luciferin) shows an inhibitory effect on the luminescence reaction of D-luciferin with firefly luciferase [ 41 , 42 ].…”