title: Dehydromicrosclerodermin B and Microsclerodermin J: Total Synthesis and Structural Revision.
abstract: The total synthesis of dehydromicrosclerodermin B and microsclerodermin J is described. Efficient approaches to the unusual amino acids in the target molecules were developed on the basis of a Negishi coupling (for Trp-2-CO2 H) and Blaise reaction (for Pyrr). An incorrect assignment of the pyrrolidinone stereochemistry of both compounds was confirmed by synthesizing epimers of the proposed structures. The spectroscopic data of these epimers were in complete agreement with those for the naturally derived material.
authors.affiliation: Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Ekaterina Y
authors.initials: EY
authors.lastname: Melikhova
authors.affiliation: Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Robert D C
authors.initials: RD
authors.lastname: Pullin
authors.affiliation: Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Christian
authors.initials: C
authors.lastname: Winter
authors.affiliation: Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK. timothy.donohoe@chem.ox.ac.uk.
authors.forename: Timothy J
authors.initials: TJ
authors.lastname: Donohoe
mesh_terms: D008968:Molecular Conformation; D010456:Peptides, Cyclic / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D010456:Peptides, Cyclic; C587943:microsclerodermin B
keywords: cross-coupling; cyclic peptides; pyrrolidinones; structure elucidation; total synthesis