(2R,3aS,4R,7S,7aR)-2-Methyl-2,3,3a,4,7,7a-hexahydro-4,7-methano-inden-1-one | 243458-59-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3aS,4R,7S,7aR)-2-Methyl-2,3,3a,4,7,7a-hexahydro-4,7-methano-inden-1-one
• 英文别名: (1S,2R,4R,6S,7R)-4-methyltricyclo[5.2.1.02,6]dec-8-en-3-one
• CAS: 243458-59-5
• 化学式: C₁₁H₁₄O
• 分子量: 162.232
• InChiKey: MBNSLLHUJWYQQF-MQIGXGKASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  (2R,3aS,4R,7S,7aR)-2-Methyl-2,3,3a,4,7,7a-hexahydro-4,7-methano-inden-1-one 在 吡啶 作用下， 以 吡啶 、 水 为溶剂， 生成 N-[4-methoxy-2-[(1S)-1-methyl-2-oxocyclopent-3-en-1-yl]phenyl]-N-methylacetamide
  参考文献：
  名称：

  7,7-Dimethyl-6,8-dioxabicyclo[3.3.0]oct-3-en-2-one as a synthetic equivalent of ketodicyclopentadiene: a new route to (−)-physostigmine, (−)-physovenine, and (−)-aphanorphine

  摘要：

  A new diastercocontrolled route to three alkaloids having a quaternary benzylic stereogenic center, (-)-physostigmine, (-)-physovenine, and (-)-aphanorphine, has been developed using enantiopure 7,7-dimethyl-6,8-dioxabicyclo[3.3.0]oct-3-en-2-one as a synthetic equivalent of chiral cyclopentadienone. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)02171-7
• 作为产物：
  描述：

  endo-tricyclo[5.2.1.0(2,6)]deca-4,8-dien-3-one 在 溶剂黄146 、 锌 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 (2R,3aS,4R,7S,7aR)-2-Methyl-2,3,3a,4,7,7a-hexahydro-4,7-methano-inden-1-one
  参考文献：
  名称：

  7,7-Dimethyl-6,8-dioxabicyclo[3.3.0]oct-3-en-2-one as a synthetic equivalent of ketodicyclopentadiene: a new route to (−)-physostigmine, (−)-physovenine, and (−)-aphanorphine

  摘要：

  A new diastercocontrolled route to three alkaloids having a quaternary benzylic stereogenic center, (-)-physostigmine, (-)-physovenine, and (-)-aphanorphine, has been developed using enantiopure 7,7-dimethyl-6,8-dioxabicyclo[3.3.0]oct-3-en-2-one as a synthetic equivalent of chiral cyclopentadienone. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)02171-7

文献信息

• Total Synthesis of (±)-Culmorin and (±)-Longiborneol:  An Efficient Construction of Tricyclo[6.3.0.0^3,9]undecan-10-one by Intramolecular Double Michael Addition
  作者：Kiyosei Takasu、Sayaka Mizutani、Miho Noguchi、Kei Makita、Masataka Ihara

  DOI：10.1021/jo000185s

  日期：2000.6.1

  TMSCl-NEt(3)-ZnCl(2) caused the intramolecular double Michael addition to afford tricyclo[6.3.0.0(3, 9)]undecan-10-one 12 in high yields with perfect stereoselectivity. The methodology was further elaborated to achieve efficient total syntheses of (+/-)-culmorin (1) and (+/-)-longiborneol (2). The common precursor 13 of them was obtained from 14 in 94% yield as a single isomer by the treatment with LHMDS. After

  用LHMDS，TMSI-HMDS，Bu（2）OTf-HMDS处理4-[（（5E）-6-甲氧羰基-5-己烯基] -3，4-二甲基-2-环戊烯-1-一（5），或TMSC1-NEt（3）-ZnCl（2）引起分子内双迈克尔加成，以高产率提供三环[6.3.0.0（3，9）] undecan-10-one 12，具有理想的立体选择性。进一步完善了该方法，以实现高效的（+/-）-culmorin（1）和（+/-）-longiborneol（2）的总合成。通过LHMDS处理，以单一异构体的形式从14以94％的产率获得它们的共同前体13。在通过水解将13转化为相应的酸24之后，使用S-（1-氧化-2-吡啶基）-1,1,3，3-四甲基硫代铀六氟磷酸盐（HOTT，27）进行氧化脱羧，然后进行桦木还原，立体选择性地提供（+/-）-culmorin（1）。通过标准转化由24个合成（+/-）-龙脑冰片（2）。另外，用
• Stereocontrolled Total Synthesis of (±)-Culmorin via the Intramolecular Double Michael Addition
  作者：Kiyosei Takasu、Sayaka Mizutani、Miho Noguchi、Kei Makita、Masataka Ihara

  DOI：10.1021/ol9900562

  日期：1999.8.1

  [GRAPHICS]We have accomplished the total synthesis of (+/-)-culmorin from the readily available ketone (11 steps, 46% overall yield). The tricyclo[6.3.0.0(3,9)]undecan-10-one skeleton, the culmorin framework, was constructed via the intramolecular double Michael addition of the cyclopentenone having an alpha beta-unsaturated ester moiety by using LHMDS, The stereochemistry of newly generated four stereogenic centers was perfectly controlled by the reaction.