methyl (R)-(+)-p-toluenesulfinylacetate | 102340-68-1

• 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: methyl (R)-(+)-p-toluenesulfinylacetate
• 英文别名: (R)-(+)-methyl-α-(para-tolylsulfinyl) acetate；methyl (+)-(R)-(p-tolylsulfinyl)acetate；methyl 2-[(R)-(4-methylphenyl)sulfinyl]acetate
• CAS: 102340-68-1
• 化学式: C₁₀H₁₂O₃S
• 分子量: 212.269
• InChiKey: OYRGZVMTNKAJPR-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  62.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (R)-(+)-p-toluenesulfinylacetate 在 silver(I) acetate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 calcium carbonate 、 碘甲烷 作用下， 以 水 、 乙腈 为溶剂， 反应 50.0h， 生成 dimethyl (-)-(2S,4S,5R,S_S)-5-(2-naphthyl)-4-(p-tolylsulfinyl)pyrrolidine-2,4-dicarboxylate
  参考文献：
  名称：

  N-金属化的甲亚胺基团与（S）-2-（对甲苯磺酰基）丙烯酸甲酯的不对称1,3-偶极环加成。光学纯的2,4,5-三取代的2,5-二氢-1H-吡咯的合成。

  摘要：

  报道了甲亚胺基化物与光学纯的乙烯基亚砜的第一1，3-偶极反应。亚磺酰基的存在增加了丙烯酸酯部分作为双极性亲和剂的反应性，并且反应以完全的区域选择性和内选择性形成。然而，分别获得了两种非对映异构体4和5的混合物（75-88％de），其分别来自反偶极/ s-顺式偶极亲和法和顺偶极/ s-反式偶极亲和法。立体选择性可以通过使用THF或MeCN作为溶剂或通过更改MeCN中的反应温度来控制。分离环加合物后，通过热解脱亚磺酰化容易获得光学纯的2，5-二氢-1H-吡咯。

  DOI：

  10.1021/jo010797s
• 作为产物：
  描述：

  Methyl 2-(4-methylphenyl)sulfinylacetate 以30%的产率得到methyl (R)-(+)-p-toluenesulfinylacetate
  参考文献：
  名称：

  ENZYME MEDIATED SYNTHESIS OF OPTICALLY ACTIVE ω-ARENESULFINYLALKANOIC ESTERS

  摘要：

  将芳基亚磺酰基乙酸甲酯和α-苯亚磺酰基丙酸甲酯与马棒杆菌 IFO 3730 一起孵育，以中等至良好的化学产率提供了高光学纯度的相应手性亚砜。

  DOI：

  10.1246/cl.1986.217

文献信息

• Studies on Chiral Organosulfur Compounds. III. Lewis Acid-Catalyzed Intramolecular Asymmetric Pericyclic Reactions of Chiral .ALPHA.-Acetyl and Methoxycarbonylvinylic Sulfoxides.
  作者：Kunio HIROI、Masayuki UMEMURA、Aki FUJISAWA

  DOI：10.1248/cpb.41.666

  日期：——

  A chiral α-sulfinyl α, β-unsaturated ketone served as a good chiral diene or enophile in intramolecular Lewis acid-catalyzed asymmetric pericyclic reactions, giving hetero-Diels-Alder reaction products, together with ene reaction products in some cases, in high optical yields. The reaction pathways for Diels-Alder or ene reactions were readily controlled depending on the Lewis acids used. A chiral α-sulfinyl α, β-unsaturated ester served as a good enophile to give ene reaction products with high enantioselectivity. The mechanistic pathway for the asymmetric induction is proposed on the basis of the stereochemical results obtained.

  一种手性的α-亚磺酰基α,β-不饱和酮在分子内路易斯酸催化的不对称周环反应中作为良好的手性二烯或亲烯，生成异源的Diels-Alder反应产物，以及在某些情况下的烯反应产物，且具有高光学产率。Diels-Alder或烯反应的反应途径可以根据所使用的路易斯酸进行有效控制。一种手性的α-亚磺酰基α,β-不饱和酯作为良好的亲烯，生成具有高对映选择性的烯反应产物。基于获得的立体化学结果，提出了不对称诱导的机制路径。
• Enzymatic Resolution and Decarboxylative Functionalization of α‐Sulfinyl Esters
  作者：Suraksha Gahalawat、Yesu Addepalli、Stephen P. Fink、Lakshmi Kasturi、Sanford D. Markowitz、Joseph M. Ready

  DOI：10.1002/chem.202302996

  日期：2024.2

  Enzymatic resolution of α-sulfinyl esters gives recovered ester and α-sulfinyl acid in high enantiomeric purity. Decarboxylative functionalization provides access to a wide range of optically active sulfoxides in both enantiomeric forms.

  α-亚爷酯的酶促分离得到具有高对映体纯度的回收酯和 α-亚爷酸。脱羧官能团化提供了两种对映体形式的多种光学活性亚砜。
• Bakers' yeast oxidation of methyl para-tolylsuifide: Synthesis of a chiral intermediate in the preparation of the mevinic acid-type hypocholestemic agents
  作者：Jenny Tang、Ian Brackenridge、Stanley M. Roberts、Jean Beecher、Andrew J. Willetts

  DOI：10.1016/0040-4020(95)00819-t

  日期：1995.11

  The use of (R)-methyl para-tolylsulfoxide as a chiral auxiliary in a novel synthesis of a key intermediate en route to mevinic acid-type hypocholestemic agents is described. The synthesis is short and simple consisting of eight steps to yield enantiomerically pure beta-silyloxy-delta-lactone. The chiral sulfoxide used in the synthesis was obtained via a straightforward biooxidation of methyl paratolylsulfide using bakers' yeast (Saccharomyces cerevisiae NCYC 73). The biotransformation involves the use of whole cells and affords the sulfoxide in good yield and with high stereoselectivity.
• Beecher, Jean; Brackenridge, Ian; Roberts, Stanley M., Journal of the Chemical Society. Perkin transactions I, 1995, # 13, p. 1641 - 1644
  作者：Beecher, Jean、Brackenridge, Ian、Roberts, Stanley M.、Tang, Jenny、Willetts, Andrew J.

  DOI：——

  日期：——
• On the applicability of the Jones active site model of pig liver esterase to S-chiral and prochiral sulfinyl substrates
  作者：Piotr Kiełbasiński

  DOI：10.1016/s0957-4166(00)00012-4

  日期：2000.3

  A series of racemic methyl sulfinylacetates was hydrolyzed in the presence of pig liver esterase (PLE) under kinetic resolution conditions to give the corresponding S-chiral sulfinylacetic acids and recovered esters in moderate enantiomeric purity. The Jones active site model was found to be suitable for explaining the enantioselectivity of the above reaction and for the PLE-mediated desymmetrization of prochiral sulfinyldicarboxylates. (C) 2000 Elsevier Science Ltd. All rights reserved.