(4'aS)-4',4'a,7',8'-tetrahydro-4'a-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalen>-5'(6'H)-one | 145632-33-3

• 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: (4'aS)-4',4'a,7',8'-tetrahydro-4'a-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalen>-5'(6'H)-one
• 英文别名: (S)-4A'-Methyl-4',4A',7',8'-tetrahydro-3'H-spiro[[1,3]dithiolane-2,2'-naphthalen]-5'(6'H)-one；(8'aS)-8'a-methylspiro[1,3-dithiolane-2,6'-3,4,7,8-tetrahydro-2H-naphthalene]-1'-one
• CAS: 145632-33-3
• 化学式: C₁₃H₁₈OS₂
• 分子量: 254.417
• InChiKey: CFIOUOSEKMDARN-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  67.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  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 thallium(III) nitrate trihydrate 、 potassium tert-butylate 、 9-硼双环[3.3.1]壬烷 、 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 2.17h， 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：

  (S)-(+)-3,4,8,8a-四氢-8a-甲基-1,6-(2H,7H)-萘醌 、 1,2-乙二硫醇 在 对甲苯磺酸 作用下， 以 溶剂黄146 为溶剂， 反应 6.0h， 以93%的产率得到(4'aS)-4',4'a,7',8'-tetrahydro-4'a-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalen>-5'(6'H)-one
  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。
• Transannular Macrocyclization via Intramolecular <i>B</i>-Alkyl Suzuki Reaction
  作者：Sherry R. Chemler、Samuel J. Danishefsky

  DOI：10.1021/ol0062547

  日期：2000.8.1

  [reaction: see text]Transannular macrocyclizations via intramolecular B-alkyl Suzuki reactions are described. Regioselective terminal olefin hydroboration with 9-BBN followed by Pd(0)-catalyzed Suzuki reaction in the presence of a base such as TlOEt at high dilution generates macrocycles with a high degree of control over olefin geometry with isomerically pure E or Z vinyl iodide substrates. These

  [反应：见正文]描述了通过分子内B-烷基Suzuki反应的环过大环化。用9-BBN进行区域选择性末端烯烃硼氢化，然后在碱（例如TlOEt）的存在下，经Pd（0）催化的Suzuki反应，以高稀释度生成大环化合物，对异构体纯的E或Z乙烯基碘化物底物具有高度的烯烃几何控制。这些反应是闭环复分解（RCM）大环化的补充，在需要控制烯烃几何形状的情况下可能证明是更好的反应。
• 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.
• An enantioselective approach to ring a of taxol using the wieland-miescher ketone
  作者：Miroslaw Golinski、Sundar Vasudevan、Rey Floresca、Carolyn P. Brock、David S. Watt

  DOI：10.1016/s0040-4039(00)60056-4

  日期：1993.1

  The selective protection of the S-(+)-enantiomer of the Wieland Miescher ketone (2) as the tertbutyldimethylsilyl-protected cyanohydrin 7 and the oxidative cleavage of an alpha-ketol 8 that was derived from 7 provided a model 10 for the A ring of the taxol (1) possessing the correct C-1 stereochemistry of taxol and functionality suitable for further elaboration.
• Addition of tert-butyldimethyl- or tert-butyldiphenylsilyl cyanide to hindered ketones
  作者：Miroslaw Golinski、Carolyn P. Brock、David S. Watt

  DOI：10.1021/jo00053a030

  日期：1993.1

  The addition of trimethylsilyl cyanide (TMSCN), tert-butyldimethylsilyl cyanide (TBDMSCN) or tert-butyldiphenylsilyl cyanide (TBDPSCN) to sterically hindered ketones proceeded in good yield under catalysis by Lewis acids (ZnI2, CH2Cl2, 25-degrees-C) or bases (KCN, 18-crown-6, CH2Cl2, 25-degrees-C). For example, the ZnI2-catalyzed addition of TBDMSCN to 2,2-dimethylcyclohexanone (3e), 2,2,6-trimethylcyclohexanone (3f), and 2,2,6,6-tetramethylcyclohexanone (3g) provided the protected cyanohydrins 4e, 4f, and 4g in 94, 83, and 92 % yield, respectively. The C-1 ketone of C-6 dithioketal-protected Wieland-Miescher ketone ((4'aS)-4',4'a,7',8'-tetrahydro-4a'-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalen]-5'(6'H)-one (+)-(8)) provided (4'aS,5'S)-4',4'a,5',6',7',8'-hexahydro-5'-[(di-methyl(1,1-dimethylethyl)silyl)oxy]-4a'-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalene]-5'-car-bonitrile (+)-(10b) in 94% yield. An X-ray crystallographic study established that the C-5 center in (+)-10b has the correct absolute stereochemistry needed for a projected synthesis of the C-1 center in the A ring of taxol using (+)-10b as a starting material.