title: Iododesilylation of TIPS-, TBDPS-, and TBS-substituted alkenes in connection with the synthesis of amphidinolides B/D.
abstract: The C-Si bonds of triisopropylsilyl-substituted alkenes, 1,3-dienes, and related multifunctional substrates, as well as analogous C-TBDPS and C-TBS bonds, are readily and chemoselectively cleaved with NIS (or other sources of I(+), such as N-iodosaccharin, 1,3-diodohydantoin, and Ipy(2)BF(4)). The desired iodoalkenes are obtained stereospecifically without byproducts, provided that the reactions are carried out in CF(3)CHOHCF(3) and, in general, with 30 mol % of Ag(2)CO(3) (or AgOAc/2,6-lutidine) as an additive. Fragment C10-C18 of cytotoxic amphidinolides B1-B3 and D has been synthesized using this improved procedure.
authors.affiliation: Departament de Química Orgànica, Facultat de Química, Universitat de Barcelona, Diagonal 647, 08028 Barcelona, Catalonia, Spain.
authors.forename: Mireia
authors.initials: M
authors.lastname: Sidera
authors.forename: Anna M
authors.initials: AM
authors.lastname: Costa
authors.forename: Jaume
authors.initials: J
authors.lastname: Vilarrasa
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism; D000097442:Amphidinolides
chemical_list: D000475:Alkenes; D019086:Bridged Bicyclo Compounds, Heterocyclic; C062197:amphidinolide D; D000097442:Amphidinolides