Desymmetrization of 4-dimethylsiloxy-1,6-heptadiynes through sequential double silylformylation.
[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.
Bonafoux
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D
Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794-3400, USA.
Ojima
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I
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
D000480:Alkynes; D012821:Silanes; D012238:Rhodium