(1S*,2S*,5R*,6R*,9R*)-2-cyclopentenyl-5,9-dimethyl-3-oxa-4-oxobicyclo<4.3.0>nonane | 134153-07-4

• 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: (1S*,2S*,5R*,6R*,9R*)-2-cyclopentenyl-5,9-dimethyl-3-oxa-4-oxobicyclo<4.3.0>nonane
• CAS: 134153-07-4；134234-84-7；134234-90-5；135027-52-0；135027-53-1；135027-55-3；135027-56-4
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: DIBIZJKDEUDDRM-YRASXDPISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.32
• 重原子数：
  17.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1S*,2S*,5R*,6R*,9R*)-2-cyclopentenyl-5,9-dimethyl-3-oxa-4-oxobicyclo<4.3.0>nonane 在 三异丁基铝 、 二异丁基氢化铝 吡啶 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 4.17h， 生成 (Z)-(3aR,5S,6R,6aR,9R,9aS)-6,9-Dimethyl-1,2,3,3a,4,5,6,6a,7,8,9,9a-dodecahydro-dicyclopenta[a,d]cycloocten-5-ol
  参考文献：
  名称：

  Alkylaluminum-catalyzed Claisen expansion reactions. Scope and stereochemistry

  摘要：

  The triisobutylaluminum-catalyzed Claisen rearrangement of a series of bicyclic allyl vinyl ethers was examined in connection with a planned synthesis of the diterpene epoxydictymene. The exocyclic vinyl ethers studied undergo [3,3] sigmatropy via chairlike transition states to provide products having Z stereochemistry about the double bond of the eight-membered ring. Differences appear only in the extent of stereoselectivity in the ensuing carbonyl reduction step. Two companion endocyclic vinyl ethers were found to utilize boat transition states to deliver Z products exclusively. In all cases, the level of chirality transfer is excellent. An analysis is presented showing that the relative configurations of the newly generated stereogenic centers, established in several key examples by X-ray crystallography, follow directly from the boat-chair options, both of which have the latent ability to be influenced catalytically by (i-Bu)3Al.

  DOI：

  10.1021/jo00012a014
• 作为产物：
  描述：

  (3aS*,4R*,6aS*)-1,3a,4,5,6,6a-hexahydro-4-methyl-2-<(trimethylsilyl)oxy>pentalene 在 六甲基磷酰三胺 、 二甲基硫 、 silica gel 、 臭氧 、 叔丁醇 、 lithium diisopropyl amide 作用下， 反应 8.08h， 生成 (1S*,2S*,5R*,6R*,9R*)-2-cyclopentenyl-5,9-dimethyl-3-oxa-4-oxobicyclo<4.3.0>nonane
  参考文献：
  名称：

  Cyclopentenyllithium additions to chiral aldehydes. Diastereofacial selectivity indicating the absence of a pronounced neighboring carboxylate anion effect

  摘要：

  The 1,2-addition of cyclopentenyllithium to a series of three five-membered aldehydo esters and their hemiacylals has been examined in order to assess the level and direction of facial selectivity surrounding nucleophilic attack at the aldehyde carbonyl and to clarify possible electronic and steric contributions stemming from neighboring functional groups. Neither methyl substitution of the acetic acid (ester) side chain nor the interchange of ester for carboxylate anion serve as important diastereocontrol elements. Instead, diastereofacial selectivity in these and related cyclic carboxaldehydes is governed by the inherent structural features of the ring system to which the functional group is attached. The convenient preparation of a complete subset of isomerically pure bicyclic lactones carrying five stereogenic centers is reported.

  DOI：

  10.1021/jo00012a013