Gastrolatathioneine, an unusual ergothioneine derivative from an aqueous extract of “tian ma”: A natural product co-produced by plant and symbiotic fungus

An unusual natural product N,N-bis(4-hydroxybenzyl)ergothioneine, named gastrolatathioneine (1), was isolated from an aqueous extract of “tian ma”, the Gastrodia elata rhizomes. Its structure was elucidated by extensive spectroscopic data analysis and confirmed by X-ray crystallography. The natural origin of 1 was proved by HPLC-ESIMS analysis of the crude extract. A biosynthetic pathway of 1 is discussed on the basis of metabolic post-modification of ergothioneine from the symbiotic fungus.