8-(benzoyloxy)-8-(methoxycarbonyl)-3-methyl-8,9,10,11-tetrahydrophenanthro<4,3-b>furan-4,5-dione | 143076-35-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 8-(benzoyloxy)-8-(methoxycarbonyl)-3-methyl-8,9,10,11-tetrahydrophenanthro<4,3-b>furan-4,5-dione
• 英文别名: methyl 8-benzoyloxy-3-methyl-4,5-dioxo-10,11-dihydro-9H-naphtho[2,1-g][1]benzofuran-8-carboxylate
• CAS: 143076-35-1
• 化学式: C₂₆H₂₀O₇
• 分子量: 444.441
• InChiKey: RVTNDMGLXKHBJN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  33
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  99.9
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  4,5-dihydro-3-methylbenzo[1,2-b]furan-4,5-dione 、 (+/-) methyl 6-(benzoyloxy)-1-vinylcyclohex-1-ene-6-carboxylate 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 生成 6-(benzoyloxy)-6-(methoxycarbonyl)-1-methyl-6,7,8,9-tetrahydrophenanthro<1,2-b>furan-10,11-dione 、 8-(benzoyloxy)-8-(methoxycarbonyl)-3-methyl-8,9,10,11-tetrahydrophenanthro<4,3-b>furan-4,5-dione
  参考文献：
  名称：

  Asymmetric synthesis of tanshindiol A.

  摘要：

  The ultrasound-promoted Diels-Alder reaction of 3-methyl-4,5-benzofurandione (10) with appropriately substituted vinylcyclohexenes has led to the synthesis of tanshindiol A (9), a minor component of the Chinese traditional medicine, Dan Shen, prepared from the roots of Salvia miltiorrhiza Bunge. The regioselectivity of the cycloaddition was enhanced by the ultrasonication and was also strongly influenced by the solvent. The asymmetric synthesis of (+)-(4R)-tanshindiol A [(+)-(4R)-91, the naturally occurring enantiomer, proceeded from the optically enriched methyl 6-(benzoyloxy)-1-vinylcyclohexene-6-carboxylate [(-)-(R)-15] or 6-hydroxy-6-(hydroxymethyl)-l-vinylcyclohexene acetonide [(+)-(R)-291 (both 92% ee). Enantioselectivity in the preparation of these diene systems was accomplished by the benzoyl peroxide quench of the lithioenamine derived from methyl 1-oxocyclohexane-2-carboxylate and (S)-valine tert-butyl ester. This procedure, adapted from Koga's asymmetric alkylation of alpha-alkyl beta-keto esters, proved highly effective in preparing the necessary tertiary alcohol in protected form and with high optical purity.

  DOI：

  10.1021/jo00046a009

文献信息

• Asymmetric synthesis of tanshindiol A.
  作者：Junning Lee、Jiahe Li、Shunichi Oya、John K. Snyder

  DOI：10.1021/jo00046a009

  日期：1992.9

  The ultrasound-promoted Diels-Alder reaction of 3-methyl-4,5-benzofurandione (10) with appropriately substituted vinylcyclohexenes has led to the synthesis of tanshindiol A (9), a minor component of the Chinese traditional medicine, Dan Shen, prepared from the roots of Salvia miltiorrhiza Bunge. The regioselectivity of the cycloaddition was enhanced by the ultrasonication and was also strongly influenced by the solvent. The asymmetric synthesis of (+)-(4R)-tanshindiol A [(+)-(4R)-91, the naturally occurring enantiomer, proceeded from the optically enriched methyl 6-(benzoyloxy)-1-vinylcyclohexene-6-carboxylate [(-)-(R)-15] or 6-hydroxy-6-(hydroxymethyl)-l-vinylcyclohexene acetonide [(+)-(R)-291 (both 92% ee). Enantioselectivity in the preparation of these diene systems was accomplished by the benzoyl peroxide quench of the lithioenamine derived from methyl 1-oxocyclohexane-2-carboxylate and (S)-valine tert-butyl ester. This procedure, adapted from Koga's asymmetric alkylation of alpha-alkyl beta-keto esters, proved highly effective in preparing the necessary tertiary alcohol in protected form and with high optical purity.