(3aS,5R,6aS)-5-methylhexahydro-2H-cyclopenta[b]furan-2-one | 1384122-53-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3aS,5R,6aS)-5-methylhexahydro-2H-cyclopenta[b]furan-2-one
• 英文别名: (3aS,5R,6aS)-5-methyl-3,3a,4,5,6,6a-hexahydrocyclopenta[b]furan-2-one
• CAS: 1384122-53-5
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: UGZFKSZPWWYPLB-VQVTYTSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3aS,5R,6aS)-5-methylhexahydro-2H-cyclopenta[b]furan-2-one 在 2,6-二甲基吡啶 、 仲丁基锂 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 30.25h， 生成 2-((1S,2S,4R)-2-((E)-6-(tert-butyldiphenylsilyloxy)-1-phenoxyhex-2-en-3-yl)-4-methyl-2-(triethylsilyloxy)cyclopentyl)-1-(pyrrolidin-1-yl)ethanone
  参考文献：
  名称：

  Total Synthesis of (+)-Sieboldine A: Evolution of a Pinacol-Terminated Cyclization Strategy

  摘要：

  This article describes synthetic studies that culminated in the first total synthesis of the Lycopodium alkaloid sieboldine A. During this study, a number of pinacol-terminated cationic cyclizations were examined to form the cis-hydrindanone core of sieboldine A. Of these, a mild Au(I)-promoted 1,6-enyne cyclization that was terminated by a semipinacol rearrangement proved to be most efficient. Fashioning the unprecedented N-hydroxyazacyclononane ring embedded within the bicyclo[5.2.1]decane-N,O-acetal moiety of sieboldine A was a formidable challenge. Ultimately, the enantioselective total synthesis of (+)-sieboldine A was completed by forming this ring in good yield by cyclization of a protected-hydroxylamine thioglycoside precursor.

  DOI：

  10.1021/jo300872y
• 作为产物：
  描述：

  (+-)-cis-3,3a,4,6a-tetrahydro-cyclopenta[b]furan-2-one 在 copper(I) bromide dimethylsulfide complex 、 二甲基硫 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 2.0h， 生成 (3aS,5R,6aS)-5-methylhexahydro-2H-cyclopenta[b]furan-2-one
  参考文献：
  名称：

  Total Synthesis of (+)-Sieboldine A: Evolution of a Pinacol-Terminated Cyclization Strategy

  摘要：

  This article describes synthetic studies that culminated in the first total synthesis of the Lycopodium alkaloid sieboldine A. During this study, a number of pinacol-terminated cationic cyclizations were examined to form the cis-hydrindanone core of sieboldine A. Of these, a mild Au(I)-promoted 1,6-enyne cyclization that was terminated by a semipinacol rearrangement proved to be most efficient. Fashioning the unprecedented N-hydroxyazacyclononane ring embedded within the bicyclo[5.2.1]decane-N,O-acetal moiety of sieboldine A was a formidable challenge. Ultimately, the enantioselective total synthesis of (+)-sieboldine A was completed by forming this ring in good yield by cyclization of a protected-hydroxylamine thioglycoside precursor.

  DOI：

  10.1021/jo300872y

文献信息

• Total Synthesis of (+)-Sieboldine A
  作者：Stephen M. Canham、David J. France、Larry E. Overman

  DOI：10.1021/ja103666n

  日期：2010.6.16

  The first total synthesis of (+)-sieboldine A was completed in 20 steps from readily available (3aS,6aR)-3,3a,4,6a-tetrahydro-2H-cyclopenta[b]furan-2-one (5). Key steps are as follows: (a) a pinacol-terminated 1,6-enyne cyclization reaction to form the cis-hydrindanone core (11 --> 12), (b) formation of the spiro tetrahydrofuran ring by stereoselective DMDO oxidation of tricyclic dihydropyran intermediate

  (+)-sieboldine A 的第一次全合成是从容易获得的 (3aS,6aR)-3,3a,4,6a-四氢-2H-环戊二烯并[b]呋喃-2-酮 (5) 分 20 步完成的。关键步骤如下：(a) 频哪醇封端的 1,6-烯炔环化反应形成顺式-氢化茚酮核心 (11 --> 12)，(b) 通过立体选择性 DMDO 氧化三环形成螺四氢呋喃环二氢吡喃中间体 15，和 (c) 通过环化硫糖苷前体 (18 --> 19) 形成前所未有的 N-羟基氮杂环壬烷环。
• Total Synthesis of (+)-Sieboldine A: Evolution of a Pinacol-Terminated Cyclization Strategy
  作者：Stephen M. Canham、David J. France、Larry E. Overman

  DOI：10.1021/jo300872y

  日期：2013.1.4

  This article describes synthetic studies that culminated in the first total synthesis of the Lycopodium alkaloid sieboldine A. During this study, a number of pinacol-terminated cationic cyclizations were examined to form the cis-hydrindanone core of sieboldine A. Of these, a mild Au(I)-promoted 1,6-enyne cyclization that was terminated by a semipinacol rearrangement proved to be most efficient. Fashioning the unprecedented N-hydroxyazacyclononane ring embedded within the bicyclo[5.2.1]decane-N,O-acetal moiety of sieboldine A was a formidable challenge. Ultimately, the enantioselective total synthesis of (+)-sieboldine A was completed by forming this ring in good yield by cyclization of a protected-hydroxylamine thioglycoside precursor.