(4S)-4-hydroxy-1-methylsulfanyl-4-(4-nitrophenyl)butan-2-one | 431046-65-0

• 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: (4S)-4-hydroxy-1-methylsulfanyl-4-(4-nitrophenyl)butan-2-one
• 英文别名: (S)-4-(4'-nitrophenyl)-4-hydroxy-1-methylsulfanyl-2-butanone；(S)-4-hydroxy-1-(methylthio)-4-(4-nitrophenyl)butan-2-one；2-Butanone, 4-hydroxy-1-(methylthio)-4-(4-nitrophenyl)-, (4S)-
• CAS: 431046-65-0
• 化学式: C₁₁H₁₃NO₄S
• 分子量: 255.295
• InChiKey: CPIUKRRVJINGPX-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  4-(4'-硝基苯基)-4-羟基-1-甲基硫烷基-2-丁酮 在 PBS buffer 作用下， 以 乙腈 为溶剂， 生成 (4S)-4-hydroxy-1-methylsulfanyl-4-(4-nitrophenyl)butan-2-one
  参考文献：
  名称：

  对映体富集的硫烷基羟醛产品的生物催化途径

  摘要：

  衍生自含硫或硒的受体的醛醇缩合产物是在抗体84G3存在下，通过对映体过量范围为56％至70％的动力学拆分制备的。对于衍生自具有三个不同受体的硫代甲氧基丙酮的硫烷基醛醇缩醛产物，其对映选择性的水平更高（对映体过量均超过96％）。

  DOI：

  10.1016/j.tet.2004.06.033

文献信息

• Recoverable silica-gel supported binam-prolinamides as organocatalysts for the enantioselective solvent-free intra- and intermolecular aldol reaction
  作者：Abraham Bañón-Caballero、Gabriela Guillena、Carmen Nájera、Enrico Faggi、Rosa María Sebastián、Adelina Vallribera

  DOI：10.1016/j.tet.2012.11.097

  日期：2013.1

  supported binam-derived prolinamides are efficient organocatalysts for the direct intramolecular and intermolecular aldol reaction under solvent-free conditions using conventional magnetic stirring. These organocatalysts in combination with benzoic acid showed similar results to those obtained under similar homogeneous reaction conditions using an organocatalyst of related structure. For the intermolecular process

  硅胶负载的比纳姆衍生的脯氨酰胺是使用常规磁力搅拌在无溶剂条件下直接进行分子内和分子间羟醛直接反应的有效有机催化剂。这些与苯甲酸组合的有机催化剂显示出与使用相关结构的有机催化剂在相似的均相反应条件下获得的结果相似的结果。对于分子间方法，羟醛产物是在室温下且仅使用2当量的酮获得的，具有高产率，区域，非对映和对映选择性。在这些反应条件下，醛之间的交叉羟醛反应也是可能的。回收的催化剂最多可重复使用九次，从而获得相似的结果。更有趣的是，
• A Highly Efficient Solvent-Free Asymmetric Direct Aldol Reaction Organocatalyzed by Recoverable (<i>S</i>)-Binam-<scp>l</scp>-Prolinamides. ESI-MS Evidence of the Enamine−Iminium Formation
  作者：Gabriela Guillena、Maria del Carmen Hita、Carmen Nájera、Santiago F. Viózquez

  DOI：10.1021/jo800773q

  日期：2008.8.1

  equiv but also the reaction time to give the aldol products with regio-, diastereo-, and enantioselectivities comparable to those in organic or aqueous solvents. Generally anti-isomers are mainly obtained with enantioselectivities up to 97%. The reaction can be carried out under these conditions also using aldehydes as nucleophiles, yielding after in situ reduction of the aldol products the corresponding

  在无溶剂反应条件下，环烷基，烷基和α-官能化的酮与醛之间的直接羟醛反应中，可回收的（S a）-二氨基-1-脯氨酰胺与苯甲酸结合用作催化剂。分析了三种不同的方法：简单的常规磁力搅拌，先前溶解于THF和蒸发后的磁力搅拌以及球磨技术。这些方法不仅可以将所需的酮量减少到2当量，而且还可以使反应时间降低，从而使醛醇产物具有与有机或水性溶剂相当的区域，非对映和对映选择性。一般反-异构体主要以高达97％的对映选择性获得。该反应也可以在这些条件下也使用醛作为亲核试剂进行，在羟醛产物原位还原后得到相应的具有中等至高对映选择性的手性1，3-二醇，主要作为抗异构体。醛醇缩合反应已通过使用正ESI-MS技术进行了研究，为形成相应的烯胺-亚胺中间体提供了证据。
• <i>N</i>-Tosyl-(<i>S</i>_a)-binam-<scp>l</scp>-prolinamide as Highly Efficient Bifunctional Organocatalyst for the General Enantioselective Solvent-Free Aldol Reaction
  作者：Gabriela Guillena、Carmen Nájera、Santiago Viózquez

  DOI：10.1055/s-0028-1087349

  日期：2008.12

  N-Tosyl-(S a)-binam-l-prolinamide (5 mol%) and benzoic acid (1 mol%) were used as catalysts in the enantioselective direct aldol reaction between different ketones and aldehydes under solvent-free conditions in the presence or absence of water. Under these reaction conditions it was possible to reduce the amount of required ketone to two equivalents to give the corresponding aldol products with high yields, regio-, diastereo- and enantioselectivities. The aldol reaction between aldehydes or the intramolecular aldol reaction can be also performed with excellent results.

  在有水或无水的无溶剂条件下，N-对甲苯磺酰基-(S a)-binam-l-脯氨酰胺（5 摩尔%）和苯甲酸（1 摩尔%）被用作催化剂，用于不同酮和醛之间的对映体选择性直接醛醇反应。在这些反应条件下，可以将所需酮的量减少到两个当量，从而得到相应的醛醇产物，并具有高产率、区域、非对映和对映选择性。醛与醛之间的醛醇反应或分子内醛醇反应也可以进行，而且效果极佳。
• Asymmetric synthesis of aldol products derived from unsymmetrical ketones: assignment of the absolute configuration of antibody aldol products
  作者：V. Maggiotti、J.-B. Wong、R. Razet、A.R. Cowley、V. Gouverneur

  DOI：10.1016/s0957-4166(02)00410-x

  日期：2002.8

  Compounds 1-7 are the products formed by aldol condensation of p-nitrobenzaldehyde with a series of unsymmetrical ketones, the reaction occurring at the less substituted carbon. The asymmetric synthesis of 1-7 using the Evans's asymmetric aldol methodology is described in detail. These syntheses were completed to allow us to assign the absolute configuration of products 1-3, obtained in a single step in the presence of the aldolase I antibody 84G3. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Unusual reversal of regioselectivity in antibody-mediated aldol additions with unsymmetrical methyl ketones
  作者：V Maggiotti、S Bahmanyar、M Reiter、M Resmini、K.N Houk、V Gouverneur

  DOI：10.1016/j.tet.2003.10.115

  日期：2004.1

  A catalytic regio- and enantioselective aldol reaction of various unsymmetrical methyl ketones with para-nitrobenzaldehyde has been developed using aldolase antibodies as the catalysts. It has been found that the sense and level of regioselectivity for the reactions catalysed by antibody 38C2 and 33F12 are highly dependent on the structure of both the donor and the acceptor but in contrast, antibodies 84G3 and 93F3 catalyse the exclusive formation of the linear regioisomer independent of the structure of the reactants examined. The level of enantiocontrol is very high for most reactions. Both linear aldol enantiomers could be accessed through aldol or retro-aldol reactions using the same antibody. Theoretical studies on regioisomeric alpha- and beta-heteroatom substituted enamines derived from unsymmetrical ketones suggest that most of the linear aldol products formed in the presence of antibodies 84G3 and 93F3 must be formed from intermediate enamines which are not the thermodynamically most favourable. (C) 2003 Elsevier Ltd. All rights reserved.