title: Substrate-dependent dihydroxylation of substituted cyclopentenes: toward the syntheses of carbocyclic sinefungin and noraristeromycin.
abstract: Carbocyclic nucleosides are of considerable interest for the development of new therapeutic agents. A key reaction in the preparation of many such nucleoside analogues is dihydroxylation of appropriately substituted cyclopentenes. Although often considered a routine reaction, in this paper, we report the dramatic influence of substituents on the facial selectivity of dihydroxylations. The substituted cyclopentene substrates are derived from acylnitroso cycloaddition reactions of cyclopentadiene, followed by N-O reduction and efficient enzymatic resolution. The results are directly utilized in a very efficient asymmetric synthesis of an antiviral carbocyclic nucleoside, noraristeromycin 5. Extensions toward the synthesis of carbocyclic sinefungin 7 document the importance of realizing the substituent dependence of the dihydroxylation reaction.
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556-5670, USA.
authors.forename: May Xiao-Wu
authors.initials: MX
authors.lastname: Jiang
authors.forename: Bohan
authors.initials: B
authors.lastname: Jin
authors.forename: Jennifer L
authors.initials: JL
authors.lastname: Gage
authors.forename: Alain
authors.initials: A
authors.lastname: Priour
authors.forename: Gordon
authors.initials: G
authors.lastname: Savela
authors.forename: Marvin J
authors.initials: MJ
authors.lastname: Miller
mesh_terms: D000241:Adenosine / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D003517:Cyclopentanes / Q000737:chemistry*; D015394:Molecular Structure; D009952:Ornithine / Q000031:analogs & derivatives* / Q000138:chemical synthesis
chemical_list: D003517:Cyclopentanes; C520120:carbocyclic sinefungin; C076829:5'-noraristeromycin; D009952:Ornithine; D000241:Adenosine; C006235:sinefungin