1-[(4S)-isopropyl-5,5-diphenyl-2-thioxo-oxazolidin-3-yl]-ethanone | 445040-77-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-[(4S)-isopropyl-5,5-diphenyl-2-thioxo-oxazolidin-3-yl]-ethanone
• 英文别名: 1-[(S)-4-isopropyl-5,5-diphenyl-2-thiooxazolidin-3-yl]ethanone；(s)-3-Acetyl-4-isopropyl-5,5-diphenyloxazolidine-2-thione；1-[(4S)-5,5-diphenyl-4-propan-2-yl-2-sulfanylidene-1,3-oxazolidin-3-yl]ethanone
• CAS: 445040-77-7
• 化学式: C₂₀H₂₁NO₂S
• 分子量: 339.458
• InChiKey: WJCFTHCUULIELA-SFHVURJKSA-N

物化性质

• 沸点：
  438.9±55.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  巴豆醛 、 1-[(4S)-isopropyl-5,5-diphenyl-2-thioxo-oxazolidin-3-yl]-ethanone 在 N-甲基吡咯烷酮 、 四氯化钛 、 鹰爪豆碱 作用下， 以 二氯甲烷 为溶剂， 反应 1.33h， 以85%的产率得到(R,E)-3-hydroxy-1-((S)-4-isopropyl-5,5-diphenyl-2-thioxooxazolidin-3-yl)hex-4-en-1-one
  参考文献：
  名称：

  实用且高度选择性的基于恶唑烷硫酮的不对称乙酸醛醇缩醛与脂肪醛的反应。

  摘要：

  [反应：见正文]据报道，缬氨酸衍生的恶唑烷硫酮可用于基于辅助剂的不对称乙酸酯醛醇缩合反应。氯化钛（IV）与（-）-天冬氨酸和N-甲基吡咯烷酮一起用于烯醇化。随后发生的与脂肪醛的醛醇缩合反应具有非对映选择性高（从92：8到99：1 dr）。

  DOI：

  10.1021/ol026108w
• 作为产物：
  描述：

  (L)-valine methyl ester hydrochloride 在 sodium hydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 28.25h， 生成 1-[(4S)-isopropyl-5,5-diphenyl-2-thioxo-oxazolidin-3-yl]-ethanone
  参考文献：
  名称：

  实用且高度选择性的基于恶唑烷硫酮的不对称乙酸醛醇缩醛与脂肪醛的反应。

  摘要：

  [反应：见正文]据报道，缬氨酸衍生的恶唑烷硫酮可用于基于辅助剂的不对称乙酸酯醛醇缩合反应。氯化钛（IV）与（-）-天冬氨酸和N-甲基吡咯烷酮一起用于烯醇化。随后发生的与脂肪醛的醛醇缩合反应具有非对映选择性高（从92：8到99：1 dr）。

  DOI：

  10.1021/ol026108w

文献信息

• Total Synthesis of the Depsipeptide FR-901375
  作者：Yanping Chen、Celine Gambs、Yoshito Abe、Paul Wentworth,、Kim D. Janda

  DOI：10.1021/jo034765b

  日期：2003.11.1

  The first total synthesis of FR-901375, a novel bicyclic depsipeptide isolated from the fermentation broth of Pseudomonas chloroaphis No. 2522, has been achieved. The synthetic approach involves 13 reaction steps and is achieved in 12% overall yield. The key points in the successful synthetic strategy are a concise asymmetric synthesis of the key building block (3R,4E)-3-hydroxy-7-mercapto-4-heptenoic

  已经实现了FR-901375的首次全合成，这是一种从绿假单胞菌第2522号发酵液中分离出的新型双环二肽。合成方法涉及13个反应步骤，总产率为12％。成功的合成策略中的关键点是关键结构单元（3R，4E）-3-羟基-7-巯基-4-庚烯酸的简明不对称合成，温和的Mitsunobu宏观内酯化步骤以及I（2）-介导的脱保护作用，同时形成二硫键。
• Total Synthesis of Solandelactones E and F, Homoeicosanoids from the Hydroid <i>Solanderia </i><i>secunda</i>
  作者：James D. White、William H. C. Martin、Christopher Lincoln、Jongtae Yang

  DOI：10.1021/ol701564x

  日期：2007.8.1

  Asymmetric total syntheses of solandelactones E and F confirmed that hydroxyl configuration at C11 in these oxylipins had been misassigned and that the stereochemistry at this center should be reversed. Key steps in the synthesis involved a Nagao asymmetric acetate aldol reaction, a directed Simmons-Smith cyclopropanation, a Holmes-Claisen rearrangement to establish the unsaturated octalactone, and

  内酯内酯E和F的不对称总合成证实，这些羟脂在C11处的羟基构型分配有误，并且该中心的立体化学应颠倒。合成中的关键步骤涉及Nagao不对称乙酸酯醛醇醛缩醛反应，定向Simmons-Smith环丙烷化，Holmes-Claisen重排以建立不饱和八内酯，以及Nozaki-Hiyama-Kishi偶联以连接C11-C12的两个主要片段。
• An Efficient Formal Synthesis of (−)-Clavosolide A Featuring a “Mismatched” Stereoselective Oxocarbenium Reduction
  作者：Jesse D. Carrick、Michael P. Jennings

  DOI：10.1021/ol8028302

  日期：2009.2.5

  The enantioselective formal synthesis of the polyketide marine natural product (−)-clavosolide A is presented. The construction of the β-C-glycoside subunit is highlighted by a one-pot oxocarbenium cation formation/reduction sequence. Yamaguchi dimerization afforded the diolide aglycon in 18 steps (longest linear sequence).

  介绍了聚酮化合物海洋天然产物（-）-clavosolide A的对映选择性形式合成。一锅氧碳glyc阳离子的形成/还原序列突出了β- C-糖苷亚基的构建。山口二聚化以18个步骤（最长的线性序列）提供了乙交酯糖苷配基。
• Enantioselective Total Synthesis of (+)-SCH 351448
  作者：Michael T. Crimmins、Grace S. Vanier

  DOI：10.1021/ol061073b

  日期：2006.6.1

  A stereoselective synthesis of SCH 351448 has been completed. Twelve of the fourteen stereogenic centers were established through chiral enolate reactions, and six key C-C bonds were formed by metathesis reactions.
• Total Synthesis of Solandelactones A, B, E, and F Exploiting a Tandem Petasis−Claisen Lactonization Strategy
  作者：James D. White、Christopher M. Lincoln、Jongtae Yang、William H. C. Martin、David B. Chan

  DOI：10.1021/jo800335g

  日期：2008.6.1

  Solandelactones A, B, E, and F were synthesized using Nozaki-Hiyania-Kishi coupling of iododiene 13 with aldehydes 14 and 99 obtained by oxidation of alcohols 92 and 94. Key steps in the synthesis of 92 and 94 were (i) a Nagao asymmetric acetate aldol reaction of aldehyde 77 with thionothiazolidine 78 to set in place an alcohol that becomes the (7S) lactone center of solandelactones, (ii) a Simmons-Smith cyclopropanation of 80 directed by this alcohol, and (iii) Petasis methylenation of cyclic carbonate 90 in tandem with a Claisen rearrangement that generates the octenalactone portion of solandelactones. Synthesis of solandelactones A, B, E, and F confirmed their gross structure and absolute configuration at C7, 8, 10, and 14 but showed that alcohol configuration at C11 must be reversed in pairs, A/B and E/F, from the previous assignment made to these hydroid metabolites. Thus, solandelactones A and B are correctly represented by 2 and 1, respectively, whereas solandelactones E and F are 6 and 5. A biogenesis of solandelactones is proposed for these C(22) oxylipins that parallels a hypothesis put forward previously to explain the origin of C(20) cyclopropane-containing algal products.