The first total synthesis of （+）-5α-hydroxy-isopterocarpolone （1）, an oxygenated eudesmane isolated from Chinese folk medicine Artemisia eriopoda, starting from （+）-dihydrocarvone（2） was described. Compound 4...The first total synthesis of （+）-5α-hydroxy-isopterocarpolone （1）, an oxygenated eudesmane isolated from Chinese folk medicine Artemisia eriopoda, starting from （+）-dihydrocarvone（2） was described. Compound 4 was stereoselectively prepared from compound 2 in three steps according to reference-. The treatment of tosylhydrazone 5, which was formed via the reaction of compound 4 and TsNHNH2 catalyzed by BF3-5Et2O, with an excess of n-butyllithium gave triene 6. Oxidation of triene 6 with singlet oxygen afforded the desired endo-peroxide 7 as a single product. Reductive cleavage of peroxide 7 with K2CO3 gave α-rotunol 3, a natural eudesmane firstly isolated in 1969. Hydrolysis of α-rotunol 3 with 10% sulfuric acid afforded （+）-5α-hydroxy-isopterocarpolone （1）. The structures of all the compounds were confirmed by IR, MS and NMR spectra.展开更多
(±)-1-Methyl-7-oxabicyclo[2.2.1]heptan-2-one (1) is a versatile chiral building block for terpenoids. It could be applied in total synthesis of eudesmanes, agarofurans and norcarotenoids. Compound (±)-1 was ...(±)-1-Methyl-7-oxabicyclo[2.2.1]heptan-2-one (1) is a versatile chiral building block for terpenoids. It could be applied in total synthesis of eudesmanes, agarofurans and norcarotenoids. Compound (±)-1 was reduced to alcohol (±)-2. Compound (±)-2 was esterified with commercial available optically pure (S)-(+)-mandelic acid. The diastereomeric ester mixture was separated with preparative HPLC method. After oxidation of the saponified products of diastereomeric ester (+)-4 and (+)-5 respectively, both optically pure enantiomers of compound 1 were prepared for the first time in four steps with an overall yield of 70%. The absolute configurations of (+)-1 and (-)-1 were determined as (+)-(1R,4S)-1-methyl-7-oxabicyclo[2.2.1] heptan-2-one and (-)-(1S,4R)-1-methyl-7-oxabicyclo[2.2.1] heptan-2-one.展开更多
文摘The first total synthesis of （+）-5α-hydroxy-isopterocarpolone （1）, an oxygenated eudesmane isolated from Chinese folk medicine Artemisia eriopoda, starting from （+）-dihydrocarvone（2） was described. Compound 4 was stereoselectively prepared from compound 2 in three steps according to reference-. The treatment of tosylhydrazone 5, which was formed via the reaction of compound 4 and TsNHNH2 catalyzed by BF3-5Et2O, with an excess of n-butyllithium gave triene 6. Oxidation of triene 6 with singlet oxygen afforded the desired endo-peroxide 7 as a single product. Reductive cleavage of peroxide 7 with K2CO3 gave α-rotunol 3, a natural eudesmane firstly isolated in 1969. Hydrolysis of α-rotunol 3 with 10% sulfuric acid afforded （+）-5α-hydroxy-isopterocarpolone （1）. The structures of all the compounds were confirmed by IR, MS and NMR spectra.
文摘(±)-1-Methyl-7-oxabicyclo[2.2.1]heptan-2-one (1) is a versatile chiral building block for terpenoids. It could be applied in total synthesis of eudesmanes, agarofurans and norcarotenoids. Compound (±)-1 was reduced to alcohol (±)-2. Compound (±)-2 was esterified with commercial available optically pure (S)-(+)-mandelic acid. The diastereomeric ester mixture was separated with preparative HPLC method. After oxidation of the saponified products of diastereomeric ester (+)-4 and (+)-5 respectively, both optically pure enantiomers of compound 1 were prepared for the first time in four steps with an overall yield of 70%. The absolute configurations of (+)-1 and (-)-1 were determined as (+)-(1R,4S)-1-methyl-7-oxabicyclo[2.2.1] heptan-2-one and (-)-(1S,4R)-1-methyl-7-oxabicyclo[2.2.1] heptan-2-one.
