(R)-3-((S)-hydroxy(phenyl)methyl)dihydro-2H-thiopyran-4-one

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

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

• 作为产物：
  描述：

  四氢噻喃-4-酮 、 苯甲醛 在 (S)-N-((1R,2R)-1,2-diphenyl-2-(phenylsulfonamido)ethyl)pyrrolidine-2-carboxamide 作用下， 以 sodium chloride 为溶剂， 生成 3-[hydroxy(phenyl)methyl]tetrahydro-4H-thiopyran-4-one 、 (3S,1'R)-3-[(1'-hydroxy-1'-phenyl)methyl]-tetrahydrothiopyran-4-one 、 (R)-3-((S)-hydroxy(phenyl)methyl)dihydro-2H-thiopyran-4-one
  参考文献：
  名称：

  衍生自氮丙啶的手性有机催化剂的合成：在不对称羟醛反应中的应用。

  摘要：

  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。

  DOI：

  10.1021/jo8019863

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。
• 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。
• Proline-catalyzed asymmetric aldol reactions of tetrahydro-4H-thiopyran-4-one with aldehydes
  作者：Dale E. Ward、Vishal Jheengut

  DOI：10.1016/j.tetlet.2004.09.061

  日期：2004.11

  Proline-catalyzed enantioselective direct intermolecular aldol reactions of tetrahydro-4H-thiopyran-4-one with various aldehydes give anti adducts with high diastereo- and enantioselectivities in moderate to excellent yields. With the aromatic aldehydes best results were obtained in wet DMF whereas dry DMSO generally was superior with the aliphatic aldehydes. Desulfurization of the adducts with Raney

  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。
• Sterically and Electronically Tunable and Bifunctional Organocatalysts:  Design and Application in Asymmetric Aldol Reaction of Cyclic Ketones with Aldehydes
  作者：Jia-Rong Chen、Xin-Yong Li、Xiao-Ning Xing、Wen-Jing Xiao

  DOI：10.1021/jo0615089

  日期：2006.10.1

  tunable and bifunctional organocatalysts have been developed and evaluated in the direct aldol reaction of heterocyclic ketones. Catalysts with different substituents showed variable catalytic efficiency for analogous substrates, indicating the importance of fine-tuning the strength of the hydrogen bonding in the two NH groups. The reactions all proceeded in good to high yield and with excellent enantioselectivities

  在杂环酮的直接醛醇缩合反应中，已经开发并评估了可立体和电子可调的双功能有机催化剂。具有不同取代基的催化剂对类似的底物显示出不同的催化效率，表明微调两个NH基团中氢键强度的重要性。反应全部以良好至高收率进行，并且具有从90％至> 99％ee的优异对映选择性。在大多数情况下，抗羟醛加合物的非对映选择性高，为96/4至99/1。
• Biheteroaromatic diphosphine oxides-catalyzed stereoselective direct aldol reactions
  作者：Sergio Rossi、Maurizio Benaglia、Andrea Genoni、Tiziana Benincori、Giuseppe Celentano

  DOI：10.1016/j.tet.2010.11.009

  日期：2011.1

  A highly stereoselective direct aldol condensation of ketones to aromatic aldehydes was realized; the trichlorosilyl enolether generated in situ in the presence of tetrachlorosilane is activated by catalytic amounts of an enantiomerically pure biheteroaromatic phosphine oxide to react with aldehydes, coordinated as well as activated by the chiral cationic hypervalent silicon species. This Lewis acid-mediated Lewis base-catalyzed transformation allowed, starting from two carbonyl compounds, to directly synthesize beta-hydroxy ketones generally with high anti stereoselectivity and up to 93% ee for the anti isomer. (C) 2010 Elsevier Ltd. All rights reserved.