Selective synthesis of chiral dioxabicyclo[4.4.0]decane and dioxabicyclo[5.3.0]decane from 3,4-bisallyloxy-but-1-yne derivatives via ruthenium-catalyzed en-yn-ene metathesis.
We prepared a series of chiral 3,4-bisallyloxy-but-1-ynes having syn and anti configurations. Treatment of these substrates with Grubbs catalyst Cl2(PCy3)2Ru=CHPh (3 mol %) preferably gave chiral dioxabicyclo[4.4.0]decane (yields > 55%) in addition to dioxabicyclo[5.3.0]decane in minor proportions. On substitution of the 4-allyloxy group of these substrates with a 4-but-2-enyloxy group, the metathesis reactions produced only dioxabicyclo[5.3.0]decane in the presence of Grubbs ruthenium-imidazolidene carbene catalyst.
D000473:Alkanes / Q000138:chemical synthesis* / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D012428:Ruthenium / Q000737:chemistry; D013237:Stereoisomerism
D000473:Alkanes; D000480:Alkynes; D000498:Allyl Compounds; D019086:Bridged Bicyclo Compounds, Heterocyclic; D012428:Ruthenium; C012867:decane