2,2-dideuterio-propionylchlorid | 37610-04-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: 2,2-dideuterio-propionylchlorid
• 英文别名: 2,2-Dideuteriopropanoyl chloride
• CAS: 37610-04-1
• 化学式: C₃H₅ClO
• 分子量: 94.5092
• InChiKey: RZWZRACFZGVKFM-CBTSVUPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  5
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2-dideuterio-propionylchlorid 、 (S)-4-苄基-2-唑烷酮 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.42h， 以71%的产率得到3-[2-2H2]-propionyl-(4S)-4-benzyl-1,3-oxazolidin-2-one
  参考文献：
  名称：

  六甲基二硅叠氮锂介导的酰化恶唑烷酮的烯醇化：溶剂、共溶剂和同位素对基于单体和二聚体的竞争途径的影响

  摘要：

  六甲基二硅肼锂 (LiHMDS) 介导的 (+)-4-benzyl-3-propionyl-2-oxazolidinone 在 THF-烃混合物中的烯醇化对烃类助溶剂（己烷与甲苯）的选择和同位素标记表现出异常的敏感性。确定了对应于单溶剂化单体、三溶剂化二聚体、八溶剂化单体和八溶剂化二聚体的四种机制。即使在 LiHMDS 单体是主要可观察形式的条件下，基于二聚体的金属化也很重要。在基态稳定和过渡态隧穿的背景下讨论了与机制有关的同位素和共溶剂效应。

  DOI：

  10.1021/jacs.6b11354
• 作为产物：
  描述：

  丙-2,2-d2酸-d 在 sodium hydroxide 、 邻苯二甲酰氯 作用下， 生成 2,2-dideuterio-propionylchlorid
  参考文献：
  名称：

  Coupled Methyl Group Epimerization and Reduction by Polyketide Synthase Ketoreductase Domains. Ketoreductase-Catalyzed Equilibrium Isotope Exchange

  摘要：

  Incubation of [2-H-2]-(2S,3R)-2-methyl-3-hydroxypentanoyl-SACP ([2-H-2]-1a) with the epimerizing ketoreductase domain EryKR1 in the presence of a catalytic amount NADP(+) (0.05 equiv) resulted in time- and cofactor-dependent washout of deuterium from la, as a result of equilibrium isotope exchange of transiently generated [2-H-2]-2-methyl-3-ketopentanoyl-ACP. Incubations of [2-H-2]-(2S,3S)-2-methyl-3-hydroxy-pentanoyl-SACP with RifKR7 and with NysKR1 also resulted in time-dependent loss of deuterium. By contrast, incubations of [2-H-2]-(2R,3S)-2-methyl-3-hydroxypentanoyl-SACP and [2-H-2]-(2R,3R)-2-methyl-3-hydroxypentanoyl-SACP with the non-epimerizing ketoreductase domains EryKR6 and TylKR1, respectively, did not result in any significant washout of deuterium. The isotope exchange assay directly establishes that specific polyketide synthase ketoreductase domains also have an intrinsic epimerase activity, thus enabling mechanistic analysis of a key determinant of polyketide stereocomplexity.

  DOI：

  10.1021/ja408944s

文献信息

• Wasserstoff/Deuterium-Isotopeneffekte bei Europium-Verschiebungsexperimenten and Allencarbonsäureestern
  作者：Robert W. Lang、Hans-Jürgen Hansen

  DOI：10.1002/hlca.19800630513

  日期：1980.7.9

  Hydrogen/Deuterium Isotope Effects on Europium Induced Chemical Shifts of Allenic Esters

  氢/氘同位素对Euro诱导的烯丙基酯化学位移的影响
• Coupled Methyl Group Epimerization and Reduction by Polyketide Synthase Ketoreductase Domains. Ketoreductase-Catalyzed Equilibrium Isotope Exchange
  作者：Ashish Garg、Chaitan Khosla、David E. Cane

  DOI：10.1021/ja408944s

  日期：2013.11.6

  Incubation of [2-H-2]-(2S,3R)-2-methyl-3-hydroxypentanoyl-SACP ([2-H-2]-1a) with the epimerizing ketoreductase domain EryKR1 in the presence of a catalytic amount NADP(+) (0.05 equiv) resulted in time- and cofactor-dependent washout of deuterium from la, as a result of equilibrium isotope exchange of transiently generated [2-H-2]-2-methyl-3-ketopentanoyl-ACP. Incubations of [2-H-2]-(2S,3S)-2-methyl-3-hydroxy-pentanoyl-SACP with RifKR7 and with NysKR1 also resulted in time-dependent loss of deuterium. By contrast, incubations of [2-H-2]-(2R,3S)-2-methyl-3-hydroxypentanoyl-SACP and [2-H-2]-(2R,3R)-2-methyl-3-hydroxypentanoyl-SACP with the non-epimerizing ketoreductase domains EryKR6 and TylKR1, respectively, did not result in any significant washout of deuterium. The isotope exchange assay directly establishes that specific polyketide synthase ketoreductase domains also have an intrinsic epimerase activity, thus enabling mechanistic analysis of a key determinant of polyketide stereocomplexity.
• Lithium Hexamethyldisilazide-Mediated Enolization of Acylated Oxazolidinones: Solvent, Cosolvent, and Isotope Effects on Competing Monomer- and Dimer-Based Pathways
  作者：Gabriel J. Reyes-Rodríguez、Russell F. Algera、David B. Collum

  DOI：10.1021/jacs.6b11354

  日期：2017.1.25

  hydrocarbon cosolvent (hexane versus toluene) and to isotopic labeling. Four mechanisms corresponding to monosolvated monomers, trisolvated dimers, octasolvated monomers, and octasolvated dimers were identified. Even under conditions in which the LiHMDS monomer was the dominant observable form, dimer-based metalation was significant. The mechanism-dependent isotope and cosolvent effects are discussed in the

  六甲基二硅肼锂 (LiHMDS) 介导的 (+)-4-benzyl-3-propionyl-2-oxazolidinone 在 THF-烃混合物中的烯醇化对烃类助溶剂（己烷与甲苯）的选择和同位素标记表现出异常的敏感性。确定了对应于单溶剂化单体、三溶剂化二聚体、八溶剂化单体和八溶剂化二聚体的四种机制。即使在 LiHMDS 单体是主要可观察形式的条件下，基于二聚体的金属化也很重要。在基态稳定和过渡态隧穿的背景下讨论了与机制有关的同位素和共溶剂效应。