(4'aR,5'S)-4',4'a,5',6',7',8'-hexahydro-4'a-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalene>-5'carboxaldehyde | 150930-57-7

• 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'aR,5'S)-4',4'a,5',6',7',8'-hexahydro-4'a-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalene>-5'carboxaldehyde
• 英文别名: (4'aR,5'S)-4',4'a,5',6',7',8'-hexahydro-4'a-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalene]-5'-carboxaldehyde；(1S,8aR)-8a-methylspiro[1,2,3,4,7,8-hexahydronaphthalene-6,2'-1,3-dithiolane]-1-carbaldehyde
• CAS: 150930-57-7
• 化学式: C₁₄H₂₀OS₂
• 分子量: 268.444
• InChiKey: INWGGQGINNPQFJ-OLZOCXBDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.79
• 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：

  乙二醇 、 (4'aR,5'S)-4',4'a,5',6',7',8'-hexahydro-4'a-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalene>-5'carboxaldehyde 在 mercury (II) perchlorate trihydrate 作用下， 以 氯仿 为溶剂， 反应 0.75h， 以67%的产率得到(4aR,5S)-5-(1,3-dioxolan-2-yl)-4a-methyl-3,4,5,6,7,8-hexahydronaphthalen-2-one
  参考文献：
  名称：

  完整酸的全合成和绝对立体化学

  摘要：

  从Wieland-Miescher酮开始，描述了一种高效的全整合酸合成方法。关键步骤涉及硫缩醛/醛的一步正交脱保护/保护策略，以及在存在其他两个不饱和部分的情况下异戊二烯基的选择性氧化裂解。完整酸的两种C4'非对映异构体的合成为C4'位置的（S）-立体化学提供了明确的证据。

  DOI：

  10.1021/jo901845r
• 作为产物：
  描述：

  (S)-(+)-3,4,8,8a-四氢-8a-甲基-1,6-(2H,7H)-萘醌 在 盐酸 、 双(三甲基硅烷基)氨基钾 、 对甲苯磺酸 作用下， 以 溶剂黄146 为溶剂， 反应 5.0h， 生成 (4'aR,5'S)-4',4'a,5',6',7',8'-hexahydro-4'a-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalene>-5'carboxaldehyde
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/ja00087a023

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。
• Non-Steroidal Antiandrogens
  申请人：Scanlan S. Thomas

  公开号：US20070049629A1

  公开（公告）日：2007-03-01

  The invention provides non-steroidal ligands for the androgen receptor, methods for making non-steroidal ligands of the androgen receptor, compositions of non-steroidal ligands of the androgen receptor and methods of using non-steroidal ligands and compositions of non-steroidal ligands of the androgen receptor for treating or preventing diseases (e.g., prostate cancer) associated with androgen binding to the androgen receptor.

  该发明提供了用于雄激素受体的非类固醇配体，制备雄激素受体非类固醇配体的方法，雄激素受体非类固醇配体的组成物以及使用非类固醇配体和雄激素受体的组成物治疗或预防与雄激素结合雄激素受体相关的疾病（例如前列腺癌）的方法。
• US9670247B2
  申请人：——

  公开号：US9670247B2

  公开（公告）日：2017-06-06
• 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.
• Total Synthesis and Absolute Stereochemistry of Integric Acid
  作者：Dennis C. J. Waalboer、Henri A. van Kalkeren、Mark C. Schaapman、Floris L. van Delft、Floris P. J. T. Rutjes

  DOI：10.1021/jo901845r

  日期：2009.11.20

  An efficient total synthesis of integric acid is described starting from the Wieland−Miescher ketone. Key steps involve a one-step orthogonal deprotection/protection strategy of a thioacetal/aldehyde and the selective oxidative cleavage of a prenyl group in the presence of two other unsaturated moieties. The synthesis of both C4′ diastereoisomers of integric acid delivered unambiguous evidence for

  从Wieland-Miescher酮开始，描述了一种高效的全整合酸合成方法。关键步骤涉及硫缩醛/醛的一步正交脱保护/保护策略，以及在存在其他两个不饱和部分的情况下异戊二烯基的选择性氧化裂解。完整酸的两种C4'非对映异构体的合成为C4'位置的（S）-立体化学提供了明确的证据。