(1'S,4'aS,8'aS)-1',4'a-dimethyl-1'-prop-2-enylspiro[1,3-dioxolane-2,5'-6,7,8,8a-tetrahydronaphthalene]-2'-one | 199525-19-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1'S,4'aS,8'aS)-1',4'a-dimethyl-1'-prop-2-enylspiro[1,3-dioxolane-2,5'-6,7,8,8a-tetrahydronaphthalene]-2'-one
• CAS: 199525-19-4
• 化学式: C₁₇H₂₄O₃
• 分子量: 276.376
• InChiKey: BEEJQKLTPLLBFX-BPUTZDHNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1'S,4'aS,8'aS)-1',4'a-dimethyl-1'-prop-2-enylspiro[1,3-dioxolane-2,5'-6,7,8,8a-tetrahydronaphthalene]-2'-one 在 potassium osmate(VI) 、 Wilkinson's catalyst 、 (DHQD)₂PYDZ 吡啶 、 咪唑 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 sodium periodate 、 正丁基锂 、 甲基磺酰胺 、 dimethyl sulfide borane 、 三氟化硼 、 四丁基氟化铵 、 甲基锂 、 碘 、 叔丁基锂 、 4-甲基苯磺酸吡啶 、 potassium carbonate 、 戴斯-马丁氧化剂 、 三苯基膦 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 乙醚 、 乙醇 、 正己烷 、 二氯甲烷 、 水 、 二甲基亚砜 、 丙酮 、 叔丁醇 、 正戊烷 、 苯 为溶剂， -78.0~65.0 ℃ 、6.89 MPa 条件下， 反应 74.08h， 生成 (+/-)-(S)-1-(furan-3-yl)-2-[(1R,2R,5S,8aS)-1,2,5-trimethyl-5-(4-methylpent-4-enyl)-1,2,3,5,6,7,8,8a-octahydro-naphthalen-1-yl]-ethanol
  参考文献：
  名称：

  Total Synthesis of Dysidiolide

  摘要：

  The cdc25A protein phosphatase inhibitor dysidiolide (1) has been synthesized enantioselectively, starting from the enantiomerically pure ketal enone 2 and using a cationic rearrangement as the key step to produce the fully substituted bicyclic core of the natural product. Once the central portion of 1 was established, elaboration of the side chains was accomplished expediently via steps that included (1) vinyl cuprate displacement of an iodide to complete the C-l side chain, (2) a highly diastereoselective oxazaborolidine-catalyzed (CBS) reduction to form carbinol 11, and (3) photochemical oxidation of 11 to generate the gamma-hydroxybutenolide functionality of 1. Additionally, this synthesis proves the absolute stereochemistry of dysidiolide (1).

  DOI：

  10.1021/ja973023v
• 作为产物：
  描述：

  (4aS)-1,4aβ-dimethyl-4,4a,7,8-tetrahydronaphthalene-2,5(3H,6H)-dione-5-ethyeneacetal 在 sodium dihydrogenphosphate 、 水 、 lithium 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 、 三甲氧基磷 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 二氯甲烷 、 氨 、 苯 为溶剂， 反应 17.67h， 生成 (1'S,4'aS,8'aS)-1',4'a-dimethyl-1'-prop-2-enylspiro[1,3-dioxolane-2,5'-6,7,8,8a-tetrahydronaphthalene]-2'-one
  参考文献：
  名称：

  Total Synthesis of Dysidiolide

  摘要：

  The cdc25A protein phosphatase inhibitor dysidiolide (1) has been synthesized enantioselectively, starting from the enantiomerically pure ketal enone 2 and using a cationic rearrangement as the key step to produce the fully substituted bicyclic core of the natural product. Once the central portion of 1 was established, elaboration of the side chains was accomplished expediently via steps that included (1) vinyl cuprate displacement of an iodide to complete the C-l side chain, (2) a highly diastereoselective oxazaborolidine-catalyzed (CBS) reduction to form carbinol 11, and (3) photochemical oxidation of 11 to generate the gamma-hydroxybutenolide functionality of 1. Additionally, this synthesis proves the absolute stereochemistry of dysidiolide (1).

  DOI：

  10.1021/ja973023v

文献信息

• Total Synthesis of Dysidiolide
  作者：E. J. Corey、Bryan E. Roberts

  DOI：10.1021/ja973023v

  日期：1997.12.1

  The cdc25A protein phosphatase inhibitor dysidiolide (1) has been synthesized enantioselectively, starting from the enantiomerically pure ketal enone 2 and using a cationic rearrangement as the key step to produce the fully substituted bicyclic core of the natural product. Once the central portion of 1 was established, elaboration of the side chains was accomplished expediently via steps that included (1) vinyl cuprate displacement of an iodide to complete the C-l side chain, (2) a highly diastereoselective oxazaborolidine-catalyzed (CBS) reduction to form carbinol 11, and (3) photochemical oxidation of 11 to generate the gamma-hydroxybutenolide functionality of 1. Additionally, this synthesis proves the absolute stereochemistry of dysidiolide (1).