((1′S,7a′R)-7a′-methyl-1′,2′,3′,6′,7′,7a′-hexahydrospiro[[1,3]dithiolane-2,5′-inden]-1′-yl)methanol | 150930-69-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: ((1′S,7a′R)-7a′-methyl-1′,2′,3′,6′,7′,7a′-hexahydrospiro[[1,3]dithiolane-2,5′-inden]-1′-yl)methanol
• CAS: 150930-69-1
• 化学式: C₁₄H₂₂OS₂
• 分子量: 270.46
• InChiKey: ROCQXWJAMOOLSL-OLZOCXBDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 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：
  0.86
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ((1′S,7a′R)-7a′-methyl-1′,2′,3′,6′,7′,7a′-hexahydrospiro[[1,3]dithiolane-2,5′-inden]-1′-yl)methanol 在 thallium(III) nitrate trihydrate 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 二甲基亚砜 为溶剂， 反应 0.17h， 生成 (1S,7aR)-7a-methyl-5-oxo-2,3,5,6,7,7a-hexahydro-1H-indene-1-carbaldehyde
  参考文献：
  名称：

  CONTRACEPTIVE AGENTS

  摘要：

  这项发明提供了式I、II、III或IV的化合物： 其中R1至R11、X和Y具有规范中定义的任何值。这些化合物抑制Na、K-ATPase α4，并可用作避孕剂。

  公开号：

  US20140005132A1
• 作为产物：
  描述：

  (4'aS)-4',4'a,7',8'-tetrahydro-4'a-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalen>-5'(6'H)-one 在 potassium tert-butylate 、 9-硼双环[3.3.1]壬烷 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 ((1′S,7a′R)-7a′-methyl-1′,2′,3′,6′,7′,7a′-hexahydrospiro[[1,3]dithiolane-2,5′-inden]-1′-yl)methanol
  参考文献：
  名称：

  CONTRACEPTIVE AGENTS

  摘要：

  这项发明提供了式I、II、III或IV的化合物： 其中R1至R11、X和Y具有规范中定义的任何值。这些化合物抑制Na、K-ATPase α4，并可用作避孕剂。

  公开号：

  US20140005132A1

文献信息

• A Ring Contraction Strategy toward a Diastereoselective Total Synthesis of (+)-Bakkenolide A
  作者：Vânia M. T. Carneiro、Helena M. C. Ferraz、Tiago O. Vieira、Eloisa E. Ishikawa、Luiz F. Silva

  DOI：10.1021/jo100108b

  日期：2010.5.7

  presented from the readily available optically active Wieland−Miescher ketone. This novel synthesis of this sesquiterpene lactone features the following as key stereoselective transformations: (i) the ring contraction reaction of a octalone mediated by thallium(III) nitrate (TTN); (ii) a hydrogenation to create the cis-fused junction; and (iii) the formation of the C7 quaternary center through an enolate intermediate

  从容易获得的旋光的Wieland-Miescher酮中可以发现非对映选择性的途径生成（+）-bakkenolideA。该倍半萜烯内酯的新颖合成具有以下作为关键的立体选择性转化的特征：（i）由硝酸th（III）（TTN）介导的八酮的环收缩反应；（ii）氢化以产生顺式-稠合的连接；（iii）通过烯醇式中间体形成C7四元中心。此外，在这项工作中，分配了从千里光腐殖质分离的三去倍半萜的绝对构型。
• Total Synthesis of the Cembranoid Diterpene Lactone (+)-Cleomeolide. Some Remarkable Conformational Features of Nine-Membered Belts Linked in 2,6-Fashion to a Methylenecyclohexane Core
  作者：Leo A. Paquette、Ting-Zhong Wang、Christophe M. G. Philippo、Shaopeng Wang

  DOI：10.1021/ja00087a023

  日期：1994.4

  The total synthesis of (+)-cleomeolide (1) has been accomplished. The key construction elements of this cembranoid lactone were (i) improved conversion of optically pure Wieland-Miescher ketone into dienol ether 12 and oxidative cleavage of the latter to aldehydo ester 13; (ii) avoidance of complications arising from steric blockade of C-15 for introduction of the methylene group at that site; (iii) exploitation of an intramolecular Wadsworth-Emmons cyclization for macrocyclic ring construction; (iv) modulation of the conformation adopted by the medium ring by diastereofacial control of epoxidation of the C-3/C-4 double bond; and (v) intramolecular cyclization of the epoxy acid derived from 27 by nucleophilic capture at the more substituted oxiranyl carbon to deliver the target molecule. The deep-seated topographical change that accompanies the formation of 29 projects the macrocyclic ring quasi-axially from the methylenecyclohexane subunit in the manner known by X-ray crystallography to be adopted by the target compound. The intramolecular cyclization to set the bridgehead double bond was thereby facilitated.
• Enantioselective synthesis of (+)-cleomeolide, the structurally unique diterpene lactone constituent of Cleome viscosa
  作者：Leo A. Paquette、Wang Ting-Zhong、Shaopeng Wang、Christophe M.G. Philippo

  DOI：10.1016/s0040-4039(00)73626-4

  日期：1993.5

  The first total synthesis of (+)-cleomeolide has been accomplished in enantioselective fashion from optically pure Wieland-Miescher ketone.