(3S,1'R)-3-[(1'-hydroxy-1'-phenyl)methyl]-tetrahydrothiopyran-4-one | 784143-65-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: (3S,1'R)-3-[(1'-hydroxy-1'-phenyl)methyl]-tetrahydrothiopyran-4-one
• 英文别名: (3S,1'S)-3-[(1'-hydroxy-1'-phenyl)methyl]-tetrahydrothiopyran-4-one；(3S)-3-[(R)-hydroxy(phenyl)methyl]tetrahydro-4H-thiopyran-4-one；(2S,1'R)-3-(hydroxy(phenyl)methyl)tetrahydrothiopyran-4-one；(S)-3-((R)-hydroxy(phenyl)methyl)-tetrahydrothiopyran-4-one；(S)-3-((R)-hydroxy(phenyl)methyl)dihydro-2H-thiopyran-4-one；(S)-tetrahydro-3-((R)-hydroxy(phenyl)methyl)thiopyran-4-one；(3S)-3-[(R)-hydroxy(phenyl)methyl]thian-4-one
• CAS: 784143-65-3
• 化学式: C₁₂H₁₄O₂S
• 分子量: 222.308
• InChiKey: SRGUURYQGCWSCT-PWSUYJOCSA-N

物化性质

• 熔点：
  126-127 °C
• 沸点：
  404.9±35.0 °C(Predicted)
• 密度：
  1.242±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  62.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,1'R)-3-[(1'-hydroxy-1'-phenyl)methyl]-tetrahydrothiopyran-4-one 在 二乙基甲氧基硼烷 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  脯氨酸催化四氢4 H-硫代吡喃-4-酮与醛的不对称醛醇缩合反应

  摘要：

  四氢-4 H-硫代吡喃-4-酮与各种醛的脯氨酸催化的对映选择性直接分子间羟醛缩合反应以中等至极好的收率得到具有高非对映体和对映体选择性的抗加合物。使用芳族醛，在湿DMF中可获得最佳结果，而干DMSO通常优于脂族醛。用阮内镍对加合物进行脱硫可提供与3-戊酮醛醇缩醛相当的产物，并可能在聚丙烯酸酯合成中得到应用。

  DOI：

  10.1016/j.tetlet.2004.09.061
• 作为产物：
  描述：

  3,6-dihydrothiopyran 4-(trimethylsilyloxy)-2H-thiopyran 在 甲基锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 (3S,1'R)-3-[(1'-hydroxy-1'-phenyl)methyl]-tetrahydrothiopyran-4-one
  参考文献：
  名称：

  The thiopyran route to polypropionates revisited: Selective syn and anti aldol reactions via 3,6-dihydro-4-trimethylsilyloxy-2H-thiopyran

  摘要：

  Aldol reaction of the amine free Li enolate of tetrahydro-4H-thiopyran-4-one with 1,4-dioxa-8-thiaspiro[4.5]decane-6-carboxaldehyde gives mainly the 2,3-anti-3,4-syn aldol(7:1) in good yield; reaction of the LDA generated lithium enolate proceeds poorly. Using the trimethylsilyl enol ether and TiCl4 gives the 2,3-syn-3,4-syn aldol(>10:1). The adducts can be used for polypropionate synthesis. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00337-7

文献信息

• Proline-Catalyzed Ketone-Aldehyde Aldol Reactions are Accelerated by Water
  作者：Petri Pihko、Annika Nyberg、Annina Usano

  DOI：10.1055/s-2004-831296

  日期：——

  Proline-catalyzed aldol reactions between acetone or 4-thianone and different aldehydes are accelerated by addition of 1-10 equivalents of water to the reaction medium, allowing stoichiometric aldol reactions to proceed at acceptable rates.

  脯氨酸催化的丙酮或四氢噻吩-4-酮与不同醛之间的羟醛反应，通过向反应体系中添加1-10当量的水，可以加速反应进程，使得定量羟醛反应能够在可接受的速率下进行。
• Primary amine-metal Lewis acid bifunctional catalysts: the application to asymmetric direct aldol reactions
  作者：Zhenghu Xu、Philias Daka、Hong Wang

  DOI：10.1039/b912728c

  日期：——

  The first example of metal Lewis acid-primary amine bifunctional cooperative catalyst derived from primary amino acids was developed, and it was found to catalyze aldol reactions of cyclic ketones highly efficiently with very good to excellent stereoselectivities.

  开发了衍生自伯氨基酸的金属路易斯酸-伯胺双官能协同催化剂的第一个实例，发现它可以非常有效地催化环状酮的醛醇缩合反应，具有非常好的至优异的立体选择性。
• Novel enantioselective direct aldol-type reaction promoted by a chiral phosphine oxide as an organocatalyst
  作者：Shunsuke Kotani、Yasushi Shimoda、Masaharu Sugiura、Makoto Nakajima

  DOI：10.1016/j.tetlet.2009.05.065

  日期：2009.8

  Chiral phosphine oxide successfully catalyzed the direct aldol-type reactions of cyclohexanone derivatives and benzaldehyde derivatives in high stereoselectivities. The reaction mechanism involves the in situ formation of trichlorosilyl enol ethers. The present reaction could be extended to the cross-aldol reactions between two aldehydes.

  手性氧化膦以高的立体选择性成功催化了环己酮衍生物和苯甲醛衍生物的直接羟醛型反应。反应机理涉及三氯甲硅烷基烯醇醚的原位形成。本反应可以扩展到两个醛之间的交叉-羟醛反应。
• Synthesis of Chiral Organocatalysts derived from Aziridines: Application in Asymmetric Aldol Reaction
  作者：Shikha Gandhi、Vinod K. Singh

  DOI：10.1021/jo8019863

  日期：2008.12.5

  We report the synthesis of a new series of highly efficient chiral organocatalysts derived via the regio- and stereoselective ring opening of chiral aziridines with azide anions. The catalysts have proved to be very efficient for a direct asymmetric aldol reaction, both with cyclic as well as acyclic ketones in brine with 2 mol % of catalyst loading, and afforded the products in excellent yields (up

  我们报告了通过手性氮丙啶与叠氮化物阴离子的区域和立体选择性开环而衍生的一系列新的高效手性有机催化剂的合成。事实证明，该催化剂对于直接与环酮和无环酮在盐水中进行直接不对称羟醛反应非常有效，催化剂负载量为2 mol％，并以极高的收率（高达99％）和对映选择性（高达到> 99％）。所获得的手性羟醛加合物通过便利的途径进一步转化为手性氮杂环丁烷环。
• Effect of additives on the proline-catalyzed ketone–aldehyde aldol reactions
  作者：Petri M. Pihko、Katri M. Laurikainen、Annina Usano、Annika I. Nyberg、Jatta A. Kaavi

  DOI：10.1016/j.tet.2005.09.070

  日期：2006.1

  The effect of bases, acids, and water as additives in proline-catalyzed ketone–aldehyde aldol reactions has been studied. While the reaction appears to be relatively tolerant to small amounts of tertiary amine bases or weak acids, it stops completely with strong acids. The use of water as an additive had a highly beneficial effect on reactions that were conducted with a stoichiometric ratio of ketone

  研究了碱，酸和水作为添加剂在脯氨酸催化的酮醛醛醇缩醛反应中的作用。尽管该反应似乎对少量的叔胺碱或弱酸具有相对的耐受性，但在强酸的作用下完全停止了。使用水作为添加剂对以酮与醛的化学计量比，特别是与环状酮进行的反应具有高度有益的效果。这允许在直接对映体选择性羟醛中有效地使用更珍贵的酮类如4-噻酮作为供体，并有助于纯化。