Acetic acid (S)-1-acetoxymethyl-2-o-tolyloxy-ethyl ester | 138710-06-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: Acetic acid (S)-1-acetoxymethyl-2-o-tolyloxy-ethyl ester
• 英文别名: [(2S)-2-acetyloxy-3-(2-methylphenoxy)propyl] acetate
• CAS: 138710-06-2
• 化学式: C₁₄H₁₈O₅
• 分子量: 266.294
• InChiKey: CVMSKRHCTWCITE-CYBMUJFWSA-N

物化性质

• 沸点：
  377.2±32.0 °C(Predicted)
• 密度：
  1.127±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Acetic acid (S)-1-acetoxymethyl-2-o-tolyloxy-ethyl ester 在 ion-exchange resin Wofatit SBW (OH(-)-form) 作用下， 以 甲醇 为溶剂， 生成 (R)-(+)-3-(2-methylphenoxy)propane-1,2-diol
  参考文献：
  名称：

  Kinetic resolution of acyclic 1,2-diols using a sequential lipase-catalyzed transesterification in organic solvents

  摘要：

  A method for the kinetic resolution of 3-(aryloxy)-1,2-propanediols rac-1a-n without additional protection-deprotection steps using a lipase-catalyzed sequential transesterification with lipase amnno PS has been developed. In the first step of this one-pot procedure the racemic 1,2-diols are acylated regioselectively at the primary hydroxy group without enantioselection. The subsequent acylation at the secondary hydroxy group of the formed primary monoacetate is responsible for high enantioselection. The enantioselectivity of this transformation depends significantly on the substitution pattern of the aryl ring and the organic solvent used. 3-(Aryloxy)-1,2-propanediols with substituents in the para-position show a much higher enantioselectivity than the corresponding derivatives with ortho-substituents. Among other substrates, the pharmaceuticals Mephenesin, Guaifenesin, and Chlorphenesin have been resolved. The replacement of the aryloxy by alkyl substituent causes a dramatic decrease of enantioselectivity.

  DOI：

  10.1021/jo00081a018
• 作为产物：
  描述：

  乙酸乙烯酯 、 甲酚甘油醚 以 四氢呋喃 为溶剂， 反应 240.0h， 以35%的产率得到Acetic acid (S)-1-acetoxymethyl-2-o-tolyloxy-ethyl ester
  参考文献：
  名称：

  Lipase-catalysed resolution of 3-(aryloxy)-1,2-propanediol derivatives — Towards an improved active site model of Pseudomonas cepacia lipase (amano PS)

  摘要：

  A variety of 3-(aryloxy)-1,2-propanediol derivatives with different substituents on the aromatic ring or at the primary hydroxy group were used as substrates in a kinetic resolution by transesterification with vinyl acetate catalysed by lipase from Pseudomonas cepacia (Amano PS). Derivatives with substituents in the para-position of the aromatic ring were accepted as substrates and resolved with high enantioselectivity. The corresponding derivatives with substituents in the ortho-position were much worse substrates for lipase PS or even non-substrates if the substituent was sufficiently space-filling as found for the tert-butyl, phenyl, benzyl or benzoyl residue. Otherwise, if the primary hydroxy group was substituted by unbranched long-chain acyl residues very good substrates were resulting. In contrast, derivatives with sterically crowded residues at the primary hydroxy group such as the pivaloyl, tert-butyldimethylsilyl, methanesulfonyl, para-toluenesulfonyl or trityl groups were nonsubstrates for lipase PS.

  DOI：

  10.1016/0957-4166(95)00166-m

文献信息

• Efficient resolution of 3-aryloxy-1,2-propanediols using CLEA-YCJ01 with high enantioselectivity
  作者：Bin Wang、Bin Wu、Bingfang He

  DOI：10.1039/c9ra01103j

  日期：——

  The lipase YCJ01 from Burkholderia ambifaria is an organic solvent-stable enzyme and its activity can be activated by a hydrophobic solvent due to the “interface activation” mechanism. The activity of lipase YCJ01 increased by 2.1-fold with t-butanol as the precipitant even after cross-linking. The cross-linked enzyme aggregates of lipase YCJ01 (CLEAs-YCJ01) were found to be efficient for resolving

  来自Burkholderia ambifaria的脂肪酶YCJ01是一种有机溶剂稳定的酶，由于“界面激活”机制，其活性可以被疏水性溶剂激活。以叔丁醇为沉淀剂，脂肪酶YCJ01交联后活性仍提高2.1倍。研究发现，脂肪酶 YCJ01 的交联酶聚集体 (CLEAs-YCJ01) 可通过顺序酯化有效分解 3-(4-甲基苯氧基)-1,2-丙二醇 (MPPD)。使用高底物浓度（180 mmol L-1）实现了对 MPPD 的优异对映选择性（E > 400），S-二乙酸盐的对映体过量 (ee) 值高达 99.2%， R-单乙酸盐的对映体过量 (ee) 值为 99.1% ，并且产率很高 (49.9%) −1 )。由此，同时获得了具有优异ee值的R型和S型化合物，并且通过CLEAs-YCJ01解决了MPPD。CLEAs-YCJ01还表现出较高的操作稳定性，十批次后仍保持91.2%的残留活性。为了进一步评估 CLEAs-YCJ01
• Kinetic resolution of rac-3-(2-methylphenoxy)propane-1,2-diol (mephenesin) by sequential lipase-catalyzed transesterification
  作者：Fritz Theil、Sibylle Ballschuh、Annamarie Kunath、Hans Schick

  DOI：10.1016/s0957-4166(00)86153-4

  日期：1991.1

  The kinetic resolution of rac-3-(2-methylphenoxy)propane-1,2-diol (rac-1, Mephenesin) by sequential lipase-catalyzed transesterification with vinyl acetate in tetrahydrofuran/triethylamine in the presence of lipase Amano PS is described.
• Kinetic resolution of acyclic 1,2-diols using a sequential lipase-catalyzed transesterification in organic solvents
  作者：Fritz Theil、Judith Weidner、Sibylle Ballschuh、Annamarie Kunath、Hans Schick

  DOI：10.1021/jo00081a018

  日期：1994.1

  A method for the kinetic resolution of 3-(aryloxy)-1,2-propanediols rac-1a-n without additional protection-deprotection steps using a lipase-catalyzed sequential transesterification with lipase amnno PS has been developed. In the first step of this one-pot procedure the racemic 1,2-diols are acylated regioselectively at the primary hydroxy group without enantioselection. The subsequent acylation at the secondary hydroxy group of the formed primary monoacetate is responsible for high enantioselection. The enantioselectivity of this transformation depends significantly on the substitution pattern of the aryl ring and the organic solvent used. 3-(Aryloxy)-1,2-propanediols with substituents in the para-position show a much higher enantioselectivity than the corresponding derivatives with ortho-substituents. Among other substrates, the pharmaceuticals Mephenesin, Guaifenesin, and Chlorphenesin have been resolved. The replacement of the aryloxy by alkyl substituent causes a dramatic decrease of enantioselectivity.
• Lipase-catalysed resolution of 3-(aryloxy)-1,2-propanediol derivatives — Towards an improved active site model of Pseudomonas cepacia lipase (amano PS)
  作者：Fritz Theil、Karin Lemke、Sibylle Ballschuh、Annamarie Kunath、Hans Schick

  DOI：10.1016/0957-4166(95)00166-m

  日期：1995.6

  A variety of 3-(aryloxy)-1,2-propanediol derivatives with different substituents on the aromatic ring or at the primary hydroxy group were used as substrates in a kinetic resolution by transesterification with vinyl acetate catalysed by lipase from Pseudomonas cepacia (Amano PS). Derivatives with substituents in the para-position of the aromatic ring were accepted as substrates and resolved with high enantioselectivity. The corresponding derivatives with substituents in the ortho-position were much worse substrates for lipase PS or even non-substrates if the substituent was sufficiently space-filling as found for the tert-butyl, phenyl, benzyl or benzoyl residue. Otherwise, if the primary hydroxy group was substituted by unbranched long-chain acyl residues very good substrates were resulting. In contrast, derivatives with sterically crowded residues at the primary hydroxy group such as the pivaloyl, tert-butyldimethylsilyl, methanesulfonyl, para-toluenesulfonyl or trityl groups were nonsubstrates for lipase PS.