Facile Retro-Dieckmann Cleavage of a Pink Phyllobilin: New Type of Potential Downstream Steps of Natural Chlorophyll Breakdown

In senescent leaves of higher plants, colourless chlorophyll (Chl) catabolites typically accumulate temporarily, and undergo natural oxidation, in part, to yellow- and pink-coloured phyllobilins (PBs). The latter, also classified as phylloroseobilins (PrBs), represent the final currently established products of Chl-breakdown, possibly playing important roles in metabolism. However, PrBs, themselves, do not accumulate in the leaves. Indeed, the original PrB identified, then classified as a pink Chl-catabolite (PiCC), is remarkably instable in methanolic solution. As reported here, PiCC readily converts at room temperature into yellow tetrapyrroles. The deduced main process, a retro-Dieckmann reaction, cleaves open its ring E moiety, the α-methoxycarbonyl-cyclopentanone unit characteristic of the Chls and of the natural Chl-derived PBs. This readily occurring reaction of the PiCC represents an unprecedented skeletal transformation of a PB, furnishing a cross-conjugated biladiene with a basic structure more similar to the heme-derived bilins.