meso-(1R,2R,4R,4aR,5S,7S,8S,8aS,9aS,10S,10aS)-1,8-Bis(acetoxymethyl)-1,3,4,5,6,7,8,8a,9,9a-decahydro-2,4,5,7,10-pentamethyl-3,6,9-trioxo-2H,10H-2,4a:7,10a-diepoxyanthracene | 301837-82-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: meso-(1R,2R,4R,4aR,5S,7S,8S,8aS,9aS,10S,10aS)-1,8-Bis(acetoxymethyl)-1,3,4,5,6,7,8,8a,9,9a-decahydro-2,4,5,7,10-pentamethyl-3,6,9-trioxo-2H,10H-2,4a:7,10a-diepoxyanthracene
• 英文别名: 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-pentamethyl-2H,10H-2,4a:7,10a-diepoxyanthracene-3,6,9(4H,5H,7H)-trione
• CAS: 301837-82-1
• 化学式: C₂₅H₃₂O₉
• 分子量: 476.524
• InChiKey: SPONFSJILQRFCT-PWNMUNBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.29
• 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：
  0.8
• 拓扑面积：
  122.27
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  meso-(1R,2R,4R,4aR,5S,7S,8S,8aS,9aS,10S,10aS)-1,8-Bis(acetoxymethyl)-1,3,4,5,6,7,8,8a,9,9a-decahydro-2,4,5,7,10-pentamethyl-3,6,9-trioxo-2H,10H-2,4a:7,10a-diepoxyanthracene 在 (R)-2-methyl-oxazaborolidine 、 四磷十氧化物 、 dimethyl sulfide borane 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 20.41h， 生成 (1R,2R,3R,4S,4aS,5S,7R,8S,9aS,10S,10aS)-1,8-bis(acetoxymethyl)-1,3,4,8,8a,9a,10,10a-octahydro-10a-hydroxy-3-(methoxymethoxy)-2,4,5,7,10-pentamethyl-2H-2,4a-epoxyanthracene-6,9-(5H,7H)-dione
  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 吡啶 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 四丙基高钌酸铵 、 dimethyl sulfide borane 、 4 A molecular sieve 、 N-甲基吗啉氧化物 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 、 乙腈 为溶剂， 25.0 ℃ 、500.0 MPa 条件下， 反应 55.25h， 生成 meso-(1R,2R,4R,4aR,5S,7S,8S,8aS,9aS,10S,10aS)-1,8-Bis(acetoxymethyl)-1,3,4,5,6,7,8,8a,9,9a-decahydro-2,4,5,7,10-pentamethyl-3,6,9-trioxo-2H,10H-2,4a:7,10a-diepoxyanthracene
  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

• Marchionni; Meilert; Vogel, Synlett, 2000, # 8, p. 1111 - 1114
  作者：Marchionni、Meilert、Vogel、Schenk

  DOI：——

  日期：——