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【结 构 式】

【分子编号】36870

【品名】methyl (2S,3S,6R)-3-(acetoxy)-6-hydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate

【CA登记号】

【 分 子 式 】C15H18O5

【 分 子 量 】278.30492

【元素组成】C 64.74% H 6.52% O 28.74%

与该中间体有关的原料药合成路线共 1 条

合成路线1

该中间体在本合成路线中的序号:(XLVI)

The enzymatic resolution of the tricyclic carboxylate (XXIX) with chiralzyme L-2 and vinyl acetate gives the monoacetate (XXX) and the dihydroxy compound (XXXI) that are easily separated. The hydrolysis of the acetate (XXX) with K2CO3 in methanol yields the diol (XLIII), which silylated with TBDMS-Cl and imidazole at the less hindered OH affording the silyl ether (XLIV). The acetylation of (XLIV) with acetyl chloride, TEA and DMAP gives the acetate (XLV), which is desilylated with TBAF in THF yielding the alcohol (XLVI). The oxidation of (XLVI) with ammonium formate and PdCl2(PPh3)2 in refluxing acetonitrile affords the ketone (XLVII), which is epoxidized with H2O2 and Triton B in THF providing the ketoepoxide (XLVIII). The thermolysis of (XLVIII) at 300 C in diphenyl ether gives the epoxycyclohexenone (II), which is reduced with NaBH4 and CeCl3 in methanol yielding a mixture of the two diastereomeric alcohols (L) and (LI) that are separated by column chromatography. The desired alcohol (LI) is treated with refluxing 80% AcOH to afford the methyl ester (XLII) of the target compound. Finally, this compound is hydrolyzed with KOH in THF. The undesired diastereomeric alcohol (L) is recycled to epoxyketone (II) by oxidation with tetrapropylammonium perruthenate (TPAP) and NMMO.

1 Yoshida, N.; Ogasawara, K.; An enatioconvergent route to (-)-shikimic acid via a palladium-mediated elimination reaction. Org Lett 2000, 2, 10, 1461.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XXIX),(XXXI) 36851 methyl (2R,3R,6S)-3,6-dihydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate C13H16O4 详情 详情
(IL) 36865 methyl (1S,6S)-5-oxo-7-oxabicyclo[4.1.0]hept-3-ene-3-carboxylate C8H8O4 详情 详情
(XIV) 29907 (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylic acid; Shikimic acid 138-59-0 C7H10O5 详情 详情
(XXX) 36852 methyl (2S,3S,6R)-6-(acetoxy)-3-hydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate C15H18O5 详情 详情
(XLII) 29908 methyl (3R,4S,5R)-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate C8H12O5 详情 详情
(XLIII) 36867 methyl (2S,3S,6R)-3,6-dihydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate C13H16O4 详情 详情
(XLIV) 36868 methyl (2S,3S,6R)-6-[[tert-butyl(dimethyl)silyl]oxy]-3-hydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate C19H30O4Si 详情 详情
(XLV) 36869 methyl (2S,3S,6R)-3-(acetoxy)-6-[[tert-butyl(dimethyl)silyl]oxy]tricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate C21H32O5Si 详情 详情
(XLVI) 36870 methyl (2S,3S,6R)-3-(acetoxy)-6-hydroxytricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate C15H18O5 详情 详情
(XLVII) 36863 methyl (2S,3S)-3-(acetoxy)-6-oxotricyclo[6.2.1.0(2,7)]undeca-4,9-diene-2-carboxylate C15H16O5 详情 详情
(XLVIII) 36864 methyl (2S,3R,4R,6S)-3-(acetoxy)-7-oxo-5-oxatetracyclo[7.2.1.0(2,8).0(4,6)]dodec-10-ene-2-carboxylate C15H16O6 详情 详情
(L) 36866 methyl (1S,5S,6R)-5-hydroxy-7-oxabicyclo[4.1.0]hept-3-ene-3-carboxylate C8H10O4 详情 详情
(LI) 29912 methyl (1S,5R,6R)-5-hydroxy-7-oxabicyclo[4.1.0]hept-3-ene-3-carboxylate C8H10O4 详情 详情
Extended Information