(R)-2-(methylsulfinyl)-1-phenylethanone | 36565-89-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-2-(methylsulfinyl)-1-phenylethanone
• 英文别名: (R)-methyl phenacyl sulfoxide；2-[(R)-methylsulfinyl]-1-phenylethanone
• CAS: 36565-89-6
• 化学式: C₉H₁₀O₂S
• 分子量: 182.243
• InChiKey: MJYVAVACHZIDHQ-GFCCVEGCSA-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

• 作为反应物：
  描述：

  甲基硫代磺酸甲酯 、 (R)-2-(methylsulfinyl)-1-phenylethanone 在 N-苄基奎宁氯 potassium carbonate 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 2.0h， 生成 (2R)-2-methylsulfanyl-2-[(R)-methylsulfinyl]-1-phenylethanone 、
  参考文献：
  名称：

  β-酮亚砜的磺酰化。三，手性相转移催化剂诱导的非对映选择性

  摘要：

  研究了在手性催化剂N-苄基奎宁鎓的存在下，在相转移催化条件下几种β-酮亚砜在亚磺酰化反应中的不对称诱导作用。结论是非对映体选择性不伴随对映体拆分。

  DOI：

  10.1016/s0040-4020(99)00705-x
• 作为产物：
  描述：

  2-methylthio-1-phenyl-ethanone 在 citrate buffer 、 chloroperoxidase from Caldariomyces fumago 、 双氧水 作用下， 反应 5.0h， 生成 (S)-methyl phenacyl sulfoxide 、 (R)-2-(methylsulfinyl)-1-phenylethanone
  参考文献：
  名称：

  Asymmetric sulfoxidation of a β-carbonyl sulfide series by chloroperoxidase

  摘要：

  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.

  DOI：

  10.1016/s0957-4166(99)00339-0

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。
• 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.
• 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.
• Sulfenylation of β-keto sulfoxides. III. Diastereoselectivity induced by a chiral phase transfer catalyst
  作者：Blanka Wladislaw、Liliana Marzorati、Francisco C. Biaggio、Reinaldo R. Vargas、Marcelo B. Bjorklund、Julio Zukerman-Schpector

  DOI：10.1016/s0040-4020(99)00705-x

  日期：1999.10

  The asymmetric induction in the sulfenylation of several β-keto sulfoxides under phase transfer catalytic conditions in the presence of the chiral catalyst N-benzylquininium chloride was investigated. It is concluded that the diastereoselectivity is not accompanied by enantiomeric resolution.

  研究了在手性催化剂N-苄基奎宁鎓的存在下，在相转移催化条件下几种β-酮亚砜在亚磺酰化反应中的不对称诱导作用。结论是非对映体选择性不伴随对映体拆分。