title: On the determination of the stereochemistry of semisynthetic natural product analogues using chiroptical spectroscopy: desulfurization of epidithiodioxopiperazine fungal metabolites.
abstract: Isolation and semisynthetic modification of the fungal metabolite chaetocin gave access to a desulfurized analogue of this natural product. Detailed chiroptical studies, comparing experimentally obtained optical rotation values, electronic circular dichroism spectra, and vibrational circular dichroism spectra to computationally simulated ones, reveal the desulfurization of chaetocin to unambiguously proceed with retention of configuration. Consideration of the plausible mechanisms for this process highlighted inconsistencies in the stereochemical assignment of related molecules in the literature. This in turn allowed the stereochemical reassignment of the natural product analogue dethiodehydrogliotoxin.
authors: Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, UK.
authors: Fanny
authors: F
authors: Cherblanc
authors: Ya-Pei
authors: YP
authors: Lo
authors: Ewoud
authors: E
authors: De Gussem
authors: Laura
authors: L
authors: Alcazar-Fuoli
authors: Elaine
authors: E
authors: Bignell
authors: Yanan
authors: Y
authors: He
authors: Nadine
authors: N
authors: Chapman-Rothe
authors: Patrick
authors: P
authors: Bultinck
authors: Wouter A
authors: WA
authors: Herrebout
authors: Robert
authors: R
authors: Brown
authors: Henry S
authors: HS
authors: Rzepa
authors: Matthew J
authors: MJ
authors: Fuchter
mesh_terms: D001688:Biological Products / Q000737:chemistry*; D002942:Circular Dichroism; D005658:Fungi / Q000378:metabolism*; D008968:Molecular Conformation; D015394:Molecular Structure; D010879:Piperazines / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013057:Spectrum Analysis; D013237:Stereoisomerism
chemical_list: D001688:Biological Products; D010879:Piperazines