(R)-o-nitrophenyl methyl sulfoxide

• 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: (R)-o-nitrophenyl methyl sulfoxide
• 英文别名: (r)-(+)-Methyl 2-nitrophenyl sulfoxide；1-[(R)-methylsulfinyl]-2-nitrobenzene
• 化学式: C₇H₇NO₃S
• 分子量: 185.203
• InChiKey: JECOZFMBKQJNDT-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：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  82.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-硝基硫代苯甲醚 在 bis(acetylacetonate)oxovanadium 、 (1S,2R)-2-((5-ethylthiophen-2-yl)methyleneamino)-1-phenylpropan-1-ol 、 双氧水 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 10.5h， 以90%的产率得到(R)-o-nitrophenyl methyl sulfoxide
  参考文献：
  名称：

  Synthesis of novel β-amino alcohols and their application in the catalytic asymmetric sulfoxidation of sulfides

  摘要：

  Novel chiral norephedrine-based beta-amino alcohol ligands containing a thiophene ring were prepared from norephedrine and substituted furan carbaldehydes (methyl- or ethyl-substituted) and used in combination with VO(acac)(2) for the asymmetric oxidation of aryl methyl sulfides using H2O2 as an oxidant. Amino alcohol derived Schiff bases 4,5a-b gave higher enantiomeric excesses than amino alcohol-derived reduced Schiff based ligands 6,7a-b. Of these chiral ligands, (1S,2R)-5b and (1S,2R)-7b gave high yields (90%) with moderate to high enantioselectivities (78%, 96% ee, respectively). The oxidation of other aryl methyl sulfides with (1S,2R)-5b and (1S,2R)-7b as ligands afforded the corresponding sulfoxides in 60-89% yields and with 92-99% ee. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.03.011

文献信息

• Efficient Asymmetric Oxidation of Sulfides and Kinetic Resolution of Sulfoxides Catalyzed by a Vanadium−Salan System
  作者：Jiangtao Sun、Chengjian Zhu、Zhenya Dai、Minghua Yang、Yi Pan、Hongwen Hu

  DOI：10.1021/jo040221d

  日期：2004.11.1

  The asymmetric oxidation of sulfides to chiral sulfoxides with hydrogen peroxide in good yield and high enantioselectivity has been catalyzed very effectively by chiral vanadium−salan [N,N‘-alkyl bis(salicylamine)] complex. The salan ligand shows results superior in terms of reactivity and enantioselectivity to those of salen [N,N‘-alkylene bis(salicylideneimine)] analogue, and provides the sulfoxide

  硫化钒以高收率和高对映选择性将硫化物不对称氧化为手性亚砜已被手性钒-Salan [ N，N'-烷基双（水杨胺）]络合物非常有效地催化。所述salan配体在反应性和对映选择性方面显示出优于salen [ N，N′-亚烷基双（水杨亚基亚胺）]类似物的结果，并提供具有相反构型的亚砜。该反应的高对映选择性是不对称氧化的直接结果。还描述了钒-salan系统催化的外消旋亚砜的有效动力学拆分。
• Asymmetric oxidation of sulfides using (salen)manganese(III) complex as a catalyst
  作者：Kenji Noda、Naoki Hosoya、Koichi Yanai、Ryo Irie、Tsutomu Katsuki

  DOI：10.1016/s0040-4039(00)73187-x

  日期：1994.3

  Asymmetric oxidation of sulfides was examined by using (salen)manganese(III) complexes as catalysts and (8S,8′S,1″S,2″S)-complex (3b) was found to show high asymmetric induction up to 90% ee. To be interested, however, (8R,8′R,1″S,2″S)-complex (1a) that showed excellent asymmetric induction in the epoxidation of simple olefins was a poor catalyst for the oxidation of sulfides.

  通过使用（salen）锰（III）配合物作为催化剂检查了硫化物的不对称氧化，发现（8 S，8 'S，1“ S，2” S）-配合物（3b）显示出高达90的高不对称感应％ee。有兴趣，但是，（8 - [R，8' - [R，1“小号，2”小号） -配合物（1A，在简单烯烃的环氧化中表现出优异的不对称诱导）是为硫化物的氧化的不良催化剂。
• Diastereoselective oxidation of menthyl arenesulfenates to sulfinates and access to enantioenriched aryl methyl sulfoxides
  作者：Matthieu Hamel、Michel Vazeux、Mihaela Gulea

  DOI：10.1007/s11696-021-01759-9

  日期：2021.11

  Three aryl methyl sulfoxides were prepared via the following sequence: synthesis of the menthyl arenesulfenate from the corresponding thiol, diastereoselective oxidation leading to the sulfinate, then reaction with a Grignard reagent. The aryl moiety was substituted with a methyl ester on the ortho position or a nitro group on the ortho or the para position. The sulfenate esters were obtained in fair

  通过以下顺序制备了三种芳基甲基亚砜：从相应的硫醇合成芳基亚磺酸薄荷酯，非对映选择性氧化得到亚磺酸盐，然后与格氏试剂反应。芳基部分被邻位上的甲酯或邻位或对位上的硝基取代。次磺酸酯的产率相当高（42-82%）。测试了四种不同的氧化剂以获得相应的亚磺酸酯，其非对映体过量 (de) 范围为 10 至 48%。在分离非对映体并与甲基格氏试剂反应后，得到两种对映体纯亚砜和一种对映体富集的亚砜（32% ee）。
• Brunei, Jean-Michel; Kagan, Henri B., Bulletin de la Societe Chimique de France, 1996, vol. 133, # 11, p. 1109 - 1115
  作者：Brunei, Jean-Michel、Kagan, Henri B.

  DOI：——

  日期：——
• Synthesis of novel β-amino alcohols and their application in the catalytic asymmetric sulfoxidation of sulfides
  作者：A. Ebru Aydin

  DOI：10.1016/j.tetasy.2013.03.011

  日期：2013.4

  Novel chiral norephedrine-based beta-amino alcohol ligands containing a thiophene ring were prepared from norephedrine and substituted furan carbaldehydes (methyl- or ethyl-substituted) and used in combination with VO(acac)(2) for the asymmetric oxidation of aryl methyl sulfides using H2O2 as an oxidant. Amino alcohol derived Schiff bases 4,5a-b gave higher enantiomeric excesses than amino alcohol-derived reduced Schiff based ligands 6,7a-b. Of these chiral ligands, (1S,2R)-5b and (1S,2R)-7b gave high yields (90%) with moderate to high enantioselectivities (78%, 96% ee, respectively). The oxidation of other aryl methyl sulfides with (1S,2R)-5b and (1S,2R)-7b as ligands afforded the corresponding sulfoxides in 60-89% yields and with 92-99% ee. (C) 2013 Elsevier Ltd. All rights reserved.