(S)-4-tert-butyl-1,3-oxazolidine-2-thione | 255828-70-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (S)-4-tert-butyl-1,3-oxazolidine-2-thione
• 英文别名: (4S)-4-tert-butyl-1,3-oxazolidine-2-thione
• CAS: 255828-70-7
• 化学式: C₇H₁₃NOS
• 分子量: 159.252
• InChiKey: DZHJLWJFPZVVDA-RXMQYKEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  53.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-4-tert-butyl-1,3-oxazolidine-2-thione 在 正丁基锂 、 四氯化钛 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.33h， 生成 (S)-4-tert-butyl-N-[(S)-2-(2,2,6,6-tetramethylpiperidin-1-yloxy)propanoyl]-1,3-oxazolidine-2-thione
  参考文献：
  名称：

  TEMPO对双自由基钛（iv）烯醇化物的一般和立体选择性氨氧化作用：手性助剂作用的详细研究†

  摘要：

  TEMPO对手性助剂对钛（IV）烯醇化物的α-氨基羟化反应的影响的综合分析表明，（S）4-叔丁基-1-恶唑烷-2-硫酮是最适合提供单一骨架的支架非对映异构体，可用于多种底物，产率高，可将这种自由基反应转化为高度化学和立体选择性的氧化反应。

  DOI：

  10.1039/c8ob01074a
• 作为产物：
  描述：

  potassium ethyl xanthogenate 、 L-叔亮氨醇 以 乙醇 为溶剂， 反应 1.0h， 以91%的产率得到(S)-4-tert-butyl-1,3-oxazolidine-2-thione
  参考文献：
  名称：

  Convenient approach to chiral 4-monosubstituted 1,3-oxazolidine-2-thiones

  摘要：

  Chiral 4-monosubstituted 1,3-oxazolidine-2-thiones are regarded as one of the modified version of Evans auxiliaries in asymmetric aldol condensation, which can generate two adjacent chiral carbon centers in one time They have advantages over Evans auxiliaries in some aspects, however, their application is highly limited by their preparation approaches as toxic or flammable chemicals are involved. Here, a mild and applicable procedure for preparing the chiral oxazolidine-2-thione auxiliaries has been developed in this article. Potassium ethylxanthate and the corresponding chiral amino alcohols as the starting material in absolute ethanol are mixed and the mixture are heated under reflux for 1h in open air to provide 1,3-oxazolidine-2-thiones chiral auxiliaries in moderate to excellent yields.[GRAPHICS].

  DOI：

  10.1080/00397911.2017.1368083

文献信息

• <i>N</i>-(Diazoacetyl)oxazolidin-2-thiones as Sulfur-Donor Reagents: Asymmetric Synthesis of Thiiranes from Aldehydes
  作者：Israel Cano、Enrique Gómez-Bengoa、Aitor Landa、Miguel Maestro、Antonia Mielgo、Iurre Olaizola、Mikel Oiarbide、Claudio Palomo

  DOI：10.1002/anie.201204771

  日期：2012.10.22

  Sulfur tyranny: Thiiranes, instead of oxiranes, can be obtained in a highly stereoselective manner through the cycloaddition reaction of N‐acyl oxazolidine tethered diazo thione compounds with aldehydes catalyzed by RhII. Thus, this reaction provides versatile adducts S functionalized at both the α and β position, with concomitant generation of two contiguous stereocenters.

  硫暴：通过N-酰基恶唑烷系链的重氮硫酮化合物与Rh II催化的醛类的环加成反应，可以以高度立体选择性的方式获得噻烷类而不是肟类。因此，该反应提供了在α和β位置均被官能化的通用加合物S，并伴随产生两个连续的立体中心。
• New Class of Pyridine Catalyst Having a Conformation Switch System:  Asymmetric Acylation of Various <i>s</i><i>ec</i>-Alcohols
  作者：Shinji Yamada、Tomoko Misono、Yuko Iwai、Ayako Masumizu、Yukiko Akiyama

  DOI：10.1021/jo060989t

  日期：2006.9.1

  new class of pyridine catalyst for asymmetric acylation of sec-alcohols having a conformation switch system in which interconversion between self-complexation and uncomplexation is induced by acylation and deacylation steps, respectively. Kinetic resolution of various sec-alcohols is performed by the asymmetric acylation with isobutyric anhydride using 0.05 to 0.5 mol % catalyst 1a with s values of up

  我们已经开发了用于具有构象转换系统的仲醇的不对称酰化的新型吡啶催化剂，在该构象转换系统中，分别通过酰化和脱酰步骤引起自复合和非复合之间的相互转化。各种仲醇的动力学拆分通过异丁酸酐的不对称酰化反应使用0.05至0.5 mol％的催化剂1a（s值最高为30）进行。此外，dl-二醇也以相似的方式以良好的选择性拆分。此外，在存在0.5-5 mol％催化剂的情况下，内消旋-1，X-二醇（X = 2-6）不对称脱对称1a。在1 H NMR测量，X射线结构分析以及AM1和DFT计算的基础上，提出了反应机理的工作模型，其中构象转换系统由吡啶环与环之间的分子内阳离子-π相互作用控制。硫羰基将在获得良好的选择性和高催化活性方面起关键作用。
• Preparation of 1,3-Thiazolidine-2-thiones by Using Potassium Ethylxanthate as a Carbon Disulfide Surrogate
  作者：Yong-Qing Yang、Zheng Lu、Weixiang Xiong

  DOI：10.1055/s-0037-1612124

  日期：2019.4

  A simple procedure is presented for preparing 1,3-thiazolidine-2-thiones by using potassium ethylxanthate and the corresponding β-amino alcohols as the starting materials in the presence of ethanol.

  介绍了以乙基黄原酸钾和相应的β-氨基醇为原料，在乙醇存在下制备1,3-噻唑烷-2-硫酮的简单方法。
• On the influence of chiral auxiliaries in the stereoselective cross-coupling reactions of titanium enolates and acetals
  作者：Jessica Baiget、Annabel Cosp、Erik Gálvez、Loreto Gómez-Pinal、Pedro Romea、Fèlix Urpí

  DOI：10.1016/j.tet.2008.04.044

  日期：2008.6

  Titanium enolates from chiral N-propanoyl-1,3-thiazolidine-2-thiones containing bulky substituents at C4 turned out to be excellent platforms to get highly stereocontrolled cross-coupling reactions with acetals. Related oxazolidinethiones also afforded good results, but the corresponding oxazolidinones resulted completely unselective for such reactions, which proves that an exocyclic C=S bond is essential to attain a synthetically useful stereocontrol. (C) 2008 Elsevier Ltd. All rights reserved.
• Asymmetric Acylation of <i>s</i><i>ec</i>-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center
  作者：Shinji Yamada、Hiroko Katsumata

  DOI：10.1021/jo990892p

  日期：1999.12.1

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.