diethyl meso-(1R,2S,3R,4R,4aR,5S,6S,7R,8S,8aS,9aR,10r,10aS)-1,3,4,5,6,7,8,8a,9,9a-decahydro-3,6-dihydroxy-2,4,5,7,10-pentamethyl-9-oxo-2H,10H-2,4a:7,10a-diepoxyanthracene-1,8-dicarboxylate | 179618-87-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: diethyl meso-(1R,2S,3R,4R,4aR,5S,6S,7R,8S,8aS,9aR,10r,10aS)-1,3,4,5,6,7,8,8a,9,9a-decahydro-3,6-dihydroxy-2,4,5,7,10-pentamethyl-9-oxo-2H,10H-2,4a:7,10a-diepoxyanthracene-1,8-dicarboxylate
• CAS: 179618-87-2
• 化学式: C₂₅H₃₆O₉
• 分子量: 480.555
• InChiKey: CDASZUQXHIVPHK-ZKPCQZNCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.87
• 重原子数：
  34.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  128.59
• 氢给体数：
  2.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  diethyl meso-(1R,2S,3R,4R,4aR,5S,6S,7R,8S,8aS,9aR,10r,10aS)-1,3,4,5,6,7,8,8a,9,9a-decahydro-3,6-dihydroxy-2,4,5,7,10-pentamethyl-9-oxo-2H,10H-2,4a:7,10a-diepoxyanthracene-1,8-dicarboxylate 在 chiral oxazaborolidine (CBS catalyst) dimethyl sulfide borane 、 3 A molecular sieve 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 生成 meso-(1R,2S,3S,4R,4aR,5S,6R,7R,8S,8aS,9aR,10r,10aS)-1,3,4,5,6,7,8,8a,9,9a-decahydro-2,4,5,7,10-pentamethyl-9-oxo-2H,10H-2,4a:7,10a-diepoxyanthracene-1,3:8,6-biscarbolactone
  参考文献：
  名称：

  Asymmetric Synthesis of Complicated Bicyclic and Tricyclic Polypropanoatesvia the DoubleDiels-Alder Addition of 2,2′-Ethylidenebis[3,5-dimethylfuran]

  摘要：

  A new, non-iterative method for the asymmetric synthesis of long-chain and polycyclic polypropanoate fragments starting from 2,2'-ethylidenebis[3,5-dimethylfuran] (2) has been developed. Diethyl (2E,5E)-4-oxohepta-2,5-dienoate (6) added to 2 to give a single meso-adduct 7 containing nine stereogenic centers. Its desymmetrization was realized by hydroboration with (+)-IpcBH(2) (isopinocampheylborane), leading to diethyl (1S,2R,3S,4S,4aS,7R,8R,8aR,9aS,10R,10aR)-1,3,4,7,8,8a,9,9a-octahydro-3-hydroxy-2,4,5,7,10-pentamethyl-9-oxo-2H,10H-2,4a : 7,10a-diepoxyanthracene-1,8-dicarboxylate ((+)-8; 78% e.e.). Alternatively, 7 was converted to meso-(1R,2R,4R,4aR,5S,7S,8S,8aR,9aS,10s,10aS)-1,8-bis(acetoxymethyl)-1,8,8a,9a-tetrahydro-2,4,5,7,10-pentamethly-2H-10H-2,4a :7,10a-diepoxyanthracene-3,6,9(4H,5H,7H)-trione (32) that was reduced enantioselectively by BH3 catalyzed by methyloxazaborolidine 19 derived form L-diphenylprolinol giving (1S,2S,4S,4aS,5S,6R,7R,8R,8aS,9aR,10R,10aS)-1,8-bis(acetoxymethyl)-1,8,8a,9a-tetrahydro-6-hydroxy-2,4,5,7,10-pentamethyl-2H,10H-2,4a :7,10a-diepoxyanthracene-3,9(4H,7H)-dione ((-)-33; 90% e.e.). Chemistry was explored to carry out chemoselective 7-oxabicylo[2.2.1]heptanone oxa-ring openings and intra-ring C-C bond cleavage. Polycclic polypropanoates as (1R,2S,3R,4R,4aR,5S,6R,7S,8R,9R,10R,11S,12aR)-1-(ethoxy-carbonyl)-1,3,4,7,8,9,10,11,12,12a-decahydro-3,11-dihydroxy-2,4,5,7,9-pentamethyl-12-oxo-2H,5H-2,4a :6,9 :6,11-triepoxybenzocyclodecene-10,8-carbolactone (51), (1S,2R,3R,4R,4aS,5S,7S,8R,9R,10R,12S,12aS)-1,10-bis(acet-oxymethyl)tetradecahydro-8-(methoxymethoxy)-2,4,5,7,9-pentamethyl-3,9-bis[[2-(trimethylsilyl)ethoxy]methoxy)-6,11-epoxycyclodecene-4a,6,11,12-tetrol((+)-83), and (1R,2R,3R,4aR,4bR,6S,6R,7R,8R,8aS,9S,10aR)-3,5-bis(acetoxymethyl)-4a,8a-dihydroxy-1-(methoxymethoxy)-2,6,8,9,10a-pentamethyl-2,7-bis([2-(trimethylsilyl)-ethoxy]methoxy)dodecahydrophenanthrene-4,10-dione (85) were obtained in few synthetic steps.

  DOI：

  10.1002/1522-2675(20010228)84:2<431::aid-hlca431>3.0.co;2-w
• 作为产物：
  描述：

  diethyl 3,5-dibromo-4-oxoheptanedioate 在 (+)-monoisopinocampheylborane 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 为溶剂， -25.0~20.0 ℃ 、500.0 MPa 条件下， 反应 66.5h， 生成 diethyl meso-(1R,2S,3R,4R,4aR,5S,6S,7R,8S,8aS,9aR,10r,10aS)-1,3,4,5,6,7,8,8a,9,9a-decahydro-3,6-dihydroxy-2,4,5,7,10-pentamethyl-9-oxo-2H,10H-2,4a:7,10a-diepoxyanthracene-1,8-dicarboxylate
  参考文献：
  名称：

  Asymmetric Synthesis of Complicated Bicyclic and Tricyclic Polypropanoatesvia the DoubleDiels-Alder Addition of 2,2′-Ethylidenebis[3,5-dimethylfuran]

  摘要：

  A new, non-iterative method for the asymmetric synthesis of long-chain and polycyclic polypropanoate fragments starting from 2,2'-ethylidenebis[3,5-dimethylfuran] (2) has been developed. Diethyl (2E,5E)-4-oxohepta-2,5-dienoate (6) added to 2 to give a single meso-adduct 7 containing nine stereogenic centers. Its desymmetrization was realized by hydroboration with (+)-IpcBH(2) (isopinocampheylborane), leading to diethyl (1S,2R,3S,4S,4aS,7R,8R,8aR,9aS,10R,10aR)-1,3,4,7,8,8a,9,9a-octahydro-3-hydroxy-2,4,5,7,10-pentamethyl-9-oxo-2H,10H-2,4a : 7,10a-diepoxyanthracene-1,8-dicarboxylate ((+)-8; 78% e.e.). Alternatively, 7 was converted to meso-(1R,2R,4R,4aR,5S,7S,8S,8aR,9aS,10s,10aS)-1,8-bis(acetoxymethyl)-1,8,8a,9a-tetrahydro-2,4,5,7,10-pentamethly-2H-10H-2,4a :7,10a-diepoxyanthracene-3,6,9(4H,5H,7H)-trione (32) that was reduced enantioselectively by BH3 catalyzed by methyloxazaborolidine 19 derived form L-diphenylprolinol giving (1S,2S,4S,4aS,5S,6R,7R,8R,8aS,9aR,10R,10aS)-1,8-bis(acetoxymethyl)-1,8,8a,9a-tetrahydro-6-hydroxy-2,4,5,7,10-pentamethyl-2H,10H-2,4a :7,10a-diepoxyanthracene-3,9(4H,7H)-dione ((-)-33; 90% e.e.). Chemistry was explored to carry out chemoselective 7-oxabicylo[2.2.1]heptanone oxa-ring openings and intra-ring C-C bond cleavage. Polycclic polypropanoates as (1R,2S,3R,4R,4aR,5S,6R,7S,8R,9R,10R,11S,12aR)-1-(ethoxy-carbonyl)-1,3,4,7,8,9,10,11,12,12a-decahydro-3,11-dihydroxy-2,4,5,7,9-pentamethyl-12-oxo-2H,5H-2,4a :6,9 :6,11-triepoxybenzocyclodecene-10,8-carbolactone (51), (1S,2R,3R,4R,4aS,5S,7S,8R,9R,10R,12S,12aS)-1,10-bis(acet-oxymethyl)tetradecahydro-8-(methoxymethoxy)-2,4,5,7,9-pentamethyl-3,9-bis[[2-(trimethylsilyl)ethoxy]methoxy)-6,11-epoxycyclodecene-4a,6,11,12-tetrol((+)-83), and (1R,2R,3R,4aR,4bR,6S,6R,7R,8R,8aS,9S,10aR)-3,5-bis(acetoxymethyl)-4a,8a-dihydroxy-1-(methoxymethoxy)-2,6,8,9,10a-pentamethyl-2,7-bis([2-(trimethylsilyl)-ethoxy]methoxy)dodecahydrophenanthrene-4,10-dione (85) were obtained in few synthetic steps.

  DOI：

  10.1002/1522-2675(20010228)84:2<431::aid-hlca431>3.0.co;2-w

文献信息

• The simultaneous double Diels-Alder addition of 1,1-bis(3,5-dimethylfur-2-yl)ethane; toward a new, asymmetric synthesis of long-chain polypropionate fragments and analogues
  作者：Chiara Marchionni、Pierre Vogel、Pietro Roversi

  DOI：10.1016/0040-4039(96)00771-x

  日期：1996.6

  The double cycloaddition of 1,1-bis(3,5-dimethylfur-2-yl)ethane to diethyl (E,E)-4-oxohepta-2,5-diene-1,7-dioate gave a single bis-adduct, the hydroboration of which with IpcBH(2) allows the creation of optically active polycyclic systems that are potential precursors of long-chain polypropionate fragments. (C) 1996 Published by Elsevier Science Ltd