title: Unprecedented influence of remote substituents on reactivity and stereoselectivity in Cu(I)-catalysed [2 + 2] photocycloaddition. An approach towards the synthesis of tricycloclavulone.
abstract: Cu(I)-catalysed [2 + 2] photocycloaddition of 1,6-dienes embedded in a furano sugar is described in connection to a synthetic approach to an abnormal marine prostanoid tricycloclavulone. An unprecedented influence of remote substituents on the reactivity and stereoselectivity of the photocycloaddition reaction has been uncovered during this investigation. While an alkene substituent inhibits cycloaddition through steric effects, a substituent having a hydroxyl or alkoxy group at the same location facilitates cycloaddition exclusively from its own side. This investigation has led to the synthesis of a functionalised 5,4-fused core unit of tricycloclavulone.
authors.affiliation: Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, 700 032, India.
authors.forename: Sujit
authors.initials: S
authors.lastname: Mondal
authors.forename: Ram Naresh
authors.initials: RN
authors.lastname: Yadav
authors.forename: Subrata
authors.initials: S
authors.lastname: Ghosh
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D003500:Cyclization; D019281:Dimerization; D015394:Molecular Structure; D055668:Photochemical Processes; D011453:Prostaglandins / Q000138:chemical synthesis*; D013237:Stereoisomerism
chemical_list: D011453:Prostaglandins; C463699:tricycloclavulone; D003300:Copper