(1S,4aS,5R,6R)-(-)-1,2,3,4,4a,5,6,7-octahydro-5-(formylmethyl)-1-(4-methyl-4-pentenyl)-1,5,6-trimethylnaphthalene | 199525-16-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,4aS,5R,6R)-(-)-1,2,3,4,4a,5,6,7-octahydro-5-(formylmethyl)-1-(4-methyl-4-pentenyl)-1,5,6-trimethylnaphthalene
• 英文别名: (1R,2R,5S,8aS)-1,2,3,5,6,7,8,8a-octahydro-1-(2-formylmethyl)-5-(4-methyl-4-pentenyl)-1,2,5-trimethylnaphthalene；2-[(1R,2R,5S,8aS)-1,2,5-trimethyl-5-(4-methylpent-4-enyl)-2,3,6,7,8,8a-hexahydronaphthalen-1-yl]acetaldehyde
• CAS: 199525-16-1
• 化学式: C₂₁H₃₄O
• 分子量: 302.5
• InChiKey: QABGUPKZZVWBKM-CWJKEVGVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S,4aS,5R,6R)-(-)-1,2,3,4,4a,5,6,7-octahydro-5-(formylmethyl)-1-(4-methyl-4-pentenyl)-1,5,6-trimethylnaphthalene 在 (S)-B-methyl CBS catalyst 吡啶 、 正丁基锂 、 dimethyl sulfide borane 、 氧气 、 rose bengal 、 戴斯-马丁氧化剂 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 18.17h， 生成 dysidiolide
  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 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 、 sodium dihydrogenphosphate 、 甲基磺酰胺 、 dimethyl sulfide borane 、 三氟化硼 、 四丁基氟化铵 、 水 、 甲基锂 、 碘 、 叔丁基锂 、 4-甲基苯磺酸吡啶 、 lithium 、 potassium carbonate 、 戴斯-马丁氧化剂 、 间氯过氧苯甲酸 、 三苯基膦 、 potassium hexacyanoferrate(III) 、 lithium diisopropyl amide 、 三甲氧基磷 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 乙醚 、 乙醇 、 二氯甲烷 、 氨 、 水 、 二甲基亚砜 、 丙酮 、 叔丁醇 、 正戊烷 、 苯 为溶剂， -78.0~90.0 ℃ 、6.89 MPa 条件下， 反应 90.75h， 生成 (1S,4aS,5R,6R)-(-)-1,2,3,4,4a,5,6,7-octahydro-5-(formylmethyl)-1-(4-methyl-4-pentenyl)-1,5,6-trimethylnaphthalene
  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 Natural Dysidiolide
  作者：Hiroaki Miyaoka、Yasuhiro Kajiwara、Yoshinori Hara、Yasuji Yamada

  DOI：10.1021/jo0015772

  日期：2001.2.1

  Dysidiolide (1), a novel sesterterpenoid previously isolated from the Caribbean sponge Dysidea etheria de Laubenfels, inhibits the action of the protein phosphatase, cdc25A. The authors establish a novel total synthesis of natural dysidiolide (1) using intramolecular Diels-Alder reaction as the key step from optically active cyclohexenone 3. Decalin, the core structure of 1, was constructed by intramolecular

  Dysidiolide（1）是一种先前从加勒比海海绵Dydya etheria de Laubenfels分离出的新型酯类萜，可抑制磷酸酶cdc25A的作用。作者以旋光性环己烯酮3为分子内Diels-Alder反应为关键步骤，建立了一种新型的天然dysidiolide（1）的全合成。通过分子内Diels-Alder反应生成的二烯酯构建了萘烷，即1，的核心结构。通过从由环己烯酮3制备的亚砜酯6中消除苯基亚砜基，在C-7处进行非对映选择性甲基化，在C-6处进行烷基化，并在C-12和C-24处进行脱氧，从而得到1的完全取代的双环核。将双环核心的两个侧链进一步延伸，以提供天然的dysidiolide（1）。
• 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).