dimethyl (1R,2R,3aS,6aS)-2,5-dihydroxy-1,2,3,3a,6,6a-hexahydropentalene-1,4-dicarboxylate | 163019-36-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: dimethyl (1R,2R,3aS,6aS)-2,5-dihydroxy-1,2,3,3a,6,6a-hexahydropentalene-1,4-dicarboxylate
• CAS: 163019-36-1
• 化学式: C₁₂H₁₆O₆
• 分子量: 256.255
• InChiKey: OKVLBTCUTUPYHZ-XZMZPDFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  93.1
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl (1R,2R,3aS,6aS)-2,5-dihydroxy-1,2,3,3a,6,6a-hexahydropentalene-1,4-dicarboxylate 在 吡啶 、 aluminum tri-bromide 、 二甲基硫 、 对甲苯磺酸 、 臭氧 、 tri-tert-butoxyaluminum hydride 作用下， 以 四氢呋喃 、 甲醇 、 苯 为溶剂， 反应 127.08h， 生成 (3aR,4R,5R,6aS)-5-乙酰氧基-2-氧代六氢-2H-环戊并[b]呋喃-4-羧酸
  参考文献：
  名称：

  A Facile Asymmetric Synthesis of Corey Lactone Utilizing C2-Symmetric Dimethyl 3,7-Dihydroxy-cis-bicyclo[3.3.0]octan-2,6-diene-2,6-dicarboxylate

  摘要：

  Optically pure Corey lactone [(-)-1] was conveniently synthesized from an optically pure C-2-symmetric diester [(+)-3] which was prepared by lipase-catalyzed demethoxycarbonylation of bicyclic tetraester (2).

  DOI：

  10.3987/com-97-s64
• 作为产物：
  描述：

  (3S,3aR,6aS)-2,5-Dihydroxy-3,3a,6,6a-tetrahydro-pentalene-1,3,4-tricarboxylic acid trimethyl ester 在 lithium hydroxide 、 sodium triethoxyborohydride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 25.0h， 生成 dimethyl (1R,2R,3aS,6aS)-2,5-dihydroxy-1,2,3,3a,6,6a-hexahydropentalene-1,4-dicarboxylate
  参考文献：
  名称：

  Lipase-catalyzed asymmetric demethoxycarbonylation: Formal syntheses of (+)-carbacyclin, (−)-ajmalicine, and (−)-tetrahydroalstonine

  摘要：

  Both enantiomers of C-2-symmetric dimethyl 3,7-dihydroxybicyclo[3.3.0]-octa-2,6-dicarboxylate 3 were prepared in enantiomerically pure form from symmetric tetraester 1 by the lipase-catalyzed demethoxycarbonylation, respectively. Double asymmetric differentiation with lipase in the above demethoxycarbonylation was observed. Their applications to formal total syntheses of (+)-carbacyclin and (-)-ajmalicine including (-)-tetrahydroalstonine are also described. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(97)00616-2

文献信息

• An asymmetric synthesis of C2-symmetric dimethyl 3,7-dioxo-cis-bicyclo[3.3.0]octane-2,6-dicarboxylate by lipase-catalyzed demethoxycarbonylation
  作者：Manabu Node、Takehisa Inoue、Mamoru Araki、Daisaku Nakamura、Kiyoharu Nishide

  DOI：10.1016/0040-4039(95)00264-d

  日期：1995.3

  Both enantiomers of C2-symmetric dimethyl 3,7-dioxo-cis-bicyclo[3.3.0]-octane-2,6-dicarboxylate (3) were prepared in enantiomerically pure form by the lipase-catalyzed demethoxycarbonylation, respectively. An expeditious formal total synthesis of (+)-carbacyclin using this hybrid process was done.

  的两种对映体c ^ 2 -对称二甲基-3,7-二氧代-顺-二环[3.3.0] -辛烷-2,6-二羧酸二（3）在对映体纯形式制备分别由脂酶催化demethoxycarbonylation。使用此混合过程可快速完成（+）-碳环素的正式全合成。
• New Asymmetric Syntheses of (-)-Isoiridomyrmecn and (+)-Loganin Aglucon 6-Acetate Utilizing C2-Symmetric Dimethyl 3,7-Dihydroxy-cis-bicyclo[3.3.0]octa-2,6-diene-2,6-dicarboxylate.
  作者：Manabu NODE、Mamoru ARAKI、Hiroaki TANAKA、Daisaku NAKAMURA、Takehisa INOUE、Kiyoharu NISHIDE

  DOI：10.1248/cpb.46.736

  日期：——

  The first asymmetric synthesis of (-)-isoiridomyrmecin and formal synthesis of (-)-loganin were done using chiral C2-symmetric building block dimethyl 3, 7-dihydroxy-cis-bicyclo[3.3.0]octa-2, 6-diene-2, 6-dicarboxylate (2) which was prepared by the lipase-catalyzed asymmetric demethoxy-carbonylation of tetramethyl 3, 7-dioxo-cis-bicyclo-[3.3.0]octane-2, 4, 6, 8-tetracarboxyrate (1).

  (-)-异伊里多霉素的首次不对称合成和(-)-洛根素的首次全合成均使用手性C2对称结构单元3,7-二羟基-顺式-双环[3.3.0]辛烷-2,6-二烯-2,6-二羧酸二甲酯（2）进行，该结构单元由四甲基3,7-二氧代-顺式-双环-[3.3.0]辛烷-2,4,6,8-四羧酸（1）经脂肪酶催化不对称脱甲氧基羰基化反应制备而成。
• A Facile Asymmetric Synthesis of Corey Lactone Utilizing C2-Symmetric Dimethyl 3,7-Dihydroxy-cis-bicyclo[3.3.0]octan-2,6-diene-2,6-dicarboxylate
  作者：Manabu Node、Daisaku Nakamura、Kiyoharu Nishide、Takehisa Inoue

  DOI：10.3987/com-97-s64

  日期：——

  Optically pure Corey lactone [(-)-1] was conveniently synthesized from an optically pure C-2-symmetric diester [(+)-3] which was prepared by lipase-catalyzed demethoxycarbonylation of bicyclic tetraester (2).
• Lipase-catalyzed asymmetric demethoxycarbonylation: Formal syntheses of (+)-carbacyclin, (−)-ajmalicine, and (−)-tetrahydroalstonine
  作者：Manabu Node、Takehisa Inoue、Mamoru Araki、Daisaku Nakamura、Kiyoharu Nishide

  DOI：10.1016/s0957-4166(97)00616-2

  日期：1998.1

  Both enantiomers of C-2-symmetric dimethyl 3,7-dihydroxybicyclo[3.3.0]-octa-2,6-dicarboxylate 3 were prepared in enantiomerically pure form from symmetric tetraester 1 by the lipase-catalyzed demethoxycarbonylation, respectively. Double asymmetric differentiation with lipase in the above demethoxycarbonylation was observed. Their applications to formal total syntheses of (+)-carbacyclin and (-)-ajmalicine including (-)-tetrahydroalstonine are also described. (C) 1998 Elsevier Science Ltd. All rights reserved.