(3S,7aS)-3a-(3-(tert-butyldiphenylsilyloxy)propyl)-6-methyl-2-methylene-3-(phenoxymethyl)hexahydro-1H-inden-4(2H)-one | 1229041-62-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (3S,7aS)-3a-(3-(tert-butyldiphenylsilyloxy)propyl)-6-methyl-2-methylene-3-(phenoxymethyl)hexahydro-1H-inden-4(2H)-one
• 英文别名: (3S,3aS,6R,7aS)-3a-[3-[tert-butyl(diphenyl)silyl]oxypropyl]-6-methyl-2-methylidene-3-(phenoxymethyl)-1,3,5,6,7,7a-hexahydroinden-4-one
• CAS: 1229041-62-6
• 化学式: C₃₇H₄₆O₃Si
• 分子量: 566.856
• InChiKey: FRSJKWOZELENFM-RAOLJYMYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  41
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  (3S,7aS)-3a-(3-(tert-butyldiphenylsilyloxy)propyl)-6-methyl-2-methylene-3-(phenoxymethyl)hexahydro-1H-inden-4(2H)-one 在 臭氧 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 生成 (7aS)-3a-(3-(tert-butyldiphenylsilyloxy)propyl)-6-methyl-3-methylenetetrahydro-1H-indene-2,4(5H,6H)-dione
  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：

  Methyl 6-(tert-butyldiphenylsiloxy)-2-hexynoate 在 2,6-二甲基吡啶 、 silver hexafluoroantimonate 、 草酰氯 、 copper(I) bromide dimethylsulfide complex 、 三苯基膦氯金 、 偶氮二甲酸二异丙酯 、 碘 、 仲丁基锂 、 二异丁基氢化铝 、 potassium carbonate 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 异丙醇 为溶剂， 反应 12.75h， 生成 (3S,7aS)-3a-(3-(tert-butyldiphenylsilyloxy)propyl)-6-methyl-2-methylene-3-(phenoxymethyl)hexahydro-1H-inden-4(2H)-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。