(S)-methyl phenacyl sulfoxide | 185547-96-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-methyl phenacyl sulfoxide
• 英文别名: Ethanone, 2-[(S)-methylsulfinyl]-1-phenyl-；2-[(S)-methylsulfinyl]-1-phenylethanone
• CAS: 185547-96-0
• 化学式: C₉H₁₀O₂S
• 分子量: 182.243
• InChiKey: MJYVAVACHZIDHQ-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  53.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  methyl phenyl ketone N,N-dimethylhydrazone 在 正丁基锂 、 phosphate buffer 、 copper dichloride 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (S)-methyl phenacyl sulfoxide
  参考文献：
  名称：

  α-甲基亚磺酰基酮的不对称合成的一般方法：在光学纯的奥苏兰和生物甾体的合成中的应用。

  摘要：

  记载了合成的免疫抑制药奥沙苏兰[1，（甲基亚磺酰基）甲基2-吡啶基酮]的首次不对称合成。使用DAG方法进行关键的缩合步骤，以光学纯净的形式高效合成了两种对映异构体。尝试将芳基甲基酮的金属烯醇盐与手性亚磺酰基化合物偶合，导致在硫上有些差向异构。通过使由这些酮衍生的N，N-二甲基hydr的α-硫代衍生物与双丙酮D-葡萄糖的（R）-或（S）-甲亚磺酸盐反应，制得相应的α- （甲基亚磺酰基）甲基hydr，在硫上具有完全的手性反转。用氯化铜（II）水解所得，得到光学纯形式的1。通过制备旋光的奥苏兰类似物2-4证明了该方法的普遍性，其中吡啶基部分分别被苯基，呋喃基和噻吩基部分取代。在研究β-酮亚砜的外消旋混合物所建立的条件下，使用手性位移试剂通过质子NMR光谱法测定这些产物的光学纯度。

  DOI：

  10.1021/jo961038q

文献信息

• Tertiary amine-catalyzed (3+3) annulations of δ-acetoxy allenoates: Substrate scope, synthetic application and mechanistic insight
  作者：Chunjie Ni、Weiping Zhou、Xiaofeng Tong

  DOI：10.1016/j.tet.2017.04.058

  日期：2017.6

  highly stereoselective synthesis of the core of calyxin I. Mechanistic experiments suggest the involvement of 3-ammonium-2,4-dienoate intermediate BN. This type of cationic intermediate arises from an addition-elimination process between allenoate substrate and amine catalyst, and is stable enough for isolation and characterization. Mechanistic studies also disclose the crucial role of amide NH of 5g

  本文报道了通过使用6'-脱氧-6'-全氟苯甲酰胺基奎宁（5g）作为催化剂，使δ-乙酰氧基烯酸酯与1C，3O-双亲核试剂进行正式（3 + 3）环化反应，可快速获得4 H-吡喃具有出色的对映选择性。该反应具有广泛的底物范围和温和的反应条件。此方法的实用性在花萼I核心的高度立体选择性合成中得到了证明。机理实验表明，3-铵-2,4-二烯酸中间体B N的参与。这种类型的阳离子中间体是由于脲基甲酸酯底物和胺催化剂之间的加成消除过程而产生的，并且对于分离和表征而言足够稳定。机理研究还透露酰胺NH的重要作用5克，这不仅能够激活allenoate便于形成乙ñ，但提高的亲电δ Ç的乙ñ亲核攻击。
• The synthesis of chiral β-ketosulfoxides by enantioselective oxidation and their stereocontrolled reduction to β-hydroxysulfoxides
  作者：Cosimo Cardellicchio、Omar Hassan Omar、Francesco Naso、Maria Annunziata M. Capozzi、Francesco Capitelli、Valerio Bertolasi

  DOI：10.1016/j.tetasy.2005.12.004

  日期：2006.1

  Various chiral non-racemic beta-ketosulfoxides, a class of compounds frequently used in asymmetric synthesis, were prepared in good yields by tert-butyl hydroperoxide oxidation of the corresponding sulfides in the presence of a complex between titanium and (S,S)-hydrobenzoin. The ee values of almost all of the purified products were > 98%. As ascertained by X-ray analysis and/or by NMR spectroscopy, the use of the (S,S)-form of the ligand led to aryl beta-ketosulfoxides with (R-S)-configuration and to methyl phenacyl sulfoxide with the (S-S)-configuration. Some of the aryl ketosulfoxides were subjected to reduction with DIBAL-H/ZnCl2 and the corresponding beta-sulfinylalcohols with an (R,R-S)-configuration produced. (c) 2005 Elsevier Ltd. All rights reserved.
• Asymmetric sulfoxidation of a β-carbonyl sulfide series by chloroperoxidase
  作者：Reinaldo R Vargas、Etelvino J.H Bechara、Liliana Marzorati、Blanka Wladislaw

  DOI：10.1016/s0957-4166(99)00339-0

  日期：1999.8

  The chloroperoxidase (CPO)-catalyzed oxidation of a series of beta-carbonyl sulfides to sulfoxides has been studied at room temperature in aqueous citrate buffer. For dialkyl beta-carbonyl sulfides, the products with methyl and ethyl substituents are obtained in ca. 100% yield. However when the alkyl group is n-propyl or i-propyl the yield drops dramatically (25%). An aryl sulfide derivative afforded product in very low yield (4%), but when the phenyl group bears a carbonyl, and the sulfur substituents are methyl or ethyl, the oxidation occurs with high yields (91-95%). Steric control of the sulfoxidation reaction is also confirmed with cyclohexanone derivatives, where a low product yield is observed even at high enzyme concentrations. Noteworthy are the yields obtained with cyclopentanone sulfide (65%) and an unexpected quantitative yield obtained with the gamma-butyrolactone sulfide. (C) 1999 Elsevier Science Ltd. All rights reserved.
• General Method for Asymmetric Synthesis of α-Methylsulfinyl Ketones:  Application to the Synthesis of Optically Pure Oxisuran and Bioisosteres
  作者：H. El Ouazzani、N. Khiar、I. Fernández、F. Alcudia

  DOI：10.1021/jo961038q

  日期：1997.1.1

  compounds led to some epimerization at sulfur. This loss of chirality was circumvented by reacting the alpha-lithio derivatives of the N,N-dimethylhydrazones derived from these ketones with either the (R)- or the (S)-methanesulfinate of diacetone D-glucose, to yield the corresponding alpha-(methylsulfinyl)methylhydrazones, with complete inversion of chirality at sulfur. Hydrolysis of the resulting

  记载了合成的免疫抑制药奥沙苏兰[1，（甲基亚磺酰基）甲基2-吡啶基酮]的首次不对称合成。使用DAG方法进行关键的缩合步骤，以光学纯净的形式高效合成了两种对映异构体。尝试将芳基甲基酮的金属烯醇盐与手性亚磺酰基化合物偶合，导致在硫上有些差向异构。通过使由这些酮衍生的N，N-二甲基hydr的α-硫代衍生物与双丙酮D-葡萄糖的（R）-或（S）-甲亚磺酸盐反应，制得相应的α- （甲基亚磺酰基）甲基hydr，在硫上具有完全的手性反转。用氯化铜（II）水解所得，得到光学纯形式的1。通过制备旋光的奥苏兰类似物2-4证明了该方法的普遍性，其中吡啶基部分分别被苯基，呋喃基和噻吩基部分取代。在研究β-酮亚砜的外消旋混合物所建立的条件下，使用手性位移试剂通过质子NMR光谱法测定这些产物的光学纯度。