title: Desymmetrization of 4-dimethylsiloxy-1,6-heptadiynes through sequential double silylformylation.
abstract: [reaction in text] Desymmetrization of dimethylsilyloxyalkadiynes (1) by Rh-catalyzed intramolecular silylformylation affords 5-exo-(formylmethylene)oxasilacyclopentanes 2 in high yields. Novel sequential double silylformylation of 1a also provides desymmetrization, giving 3-(3-silyl-2-formylprop-2-enyl)-5-exo-(formylmethylene)oxasilacyclopentanes 4 in excellent yields. Reduction of 2a and 4 with NaBH(4) gives the corresponding 5-exo-(hydroxymethylmethylene)oxasilacyclopentanes 3a and 5, respectively.
authors.affiliation: Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794-3400, USA.
authors.forename: D
authors.initials: D
authors.lastname: Bonafoux
authors.forename: I
authors.initials: I
authors.lastname: Ojima
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry*; D013329:Structure-Activity Relationship
chemical_list: D000480:Alkynes; D012821:Silanes; D012238:Rhodium