title: Total Synthesis of the GRP78-Downregulatory Macrolide (+)-Prunustatin A, the Immunosuppressant (+)-SW-163A, and a JBIR-04 Diastereoisomer That Confirms JBIR-04 Has Nonidentical Stereochemistry to (+)-Prunustatin A.
abstract: A unified total synthesis of the GRP78-downregulator (+)-prunustatin A and the immunosuppressant (+)-SW-163A based upon [1 + 1 + 1 + 1]-fragment condensation and macrolactonization between O(4) and C(5) is herein described. Sharpless asymmetric dihydroxylation was used to set the C(2) stereocenter present in both targets. In like fashion, coupling of the (+)-prunustatin A macrolide amine with benzoic acid furnished a JBIR-04 diastereoisomer whose NMR spectra did not match those of JBIR-04, thus confirming that it has different stereochemistry than (+)-prunustatin A.
authors.affiliation: School of Chemistry & Chemical Engineering and Centre for Cancer Research and Cell Biology (CCRCB), Queen's University Belfast , Stranmillis Road, Belfast BT9 5AG, Northern Ireland, United Kingdom.
authors.forename: Soraya
authors.initials: S
authors.lastname: Manaviazar
authors.affiliation: School of Chemistry & Chemical Engineering and Centre for Cancer Research and Cell Biology (CCRCB), Queen's University Belfast , Stranmillis Road, Belfast BT9 5AG, Northern Ireland, United Kingdom.
authors.forename: Peter
authors.initials: P
authors.lastname: Nockemann
authors.affiliation: School of Chemistry & Chemical Engineering and Centre for Cancer Research and Cell Biology (CCRCB), Queen's University Belfast , Stranmillis Road, Belfast BT9 5AG, Northern Ireland, United Kingdom.
authors.forename: Karl J
authors.initials: KJ
authors.lastname: Hale
mesh_terms: D002384:Catalysis; D003500:Cyclization; D000091342:Endoplasmic Reticulum Chaperone BiP; D006360:Heat-Shock Proteins / Q000378:metabolism*; D007166:Immunosuppressive Agents / Q000138:chemical synthesis*; D018942:Macrolides / Q000138:chemical synthesis*; D010456:Peptides, Cyclic / Q000138:chemical synthesis*; D013237:Stereoisomerism
chemical_list: D000091342:Endoplasmic Reticulum Chaperone BiP; D006360:Heat-Shock Proteins; D007166:Immunosuppressive Agents; C526002:JBIR-04; D018942:Macrolides; D010456:Peptides, Cyclic; C447401:SW-163A; C501241:prunustatin A