dimethyl 2-(diisopropylamino)propanedioate | 372191-56-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl 2-(diisopropylamino)propanedioate
• 英文别名: Dimethyl 2-[di(propan-2-yl)amino]propanedioate
• CAS: 372191-56-5
• 化学式: C₁₁H₂₁NO₄
• 分子量: 231.292
• InChiKey: MZEQNUGMEZXISM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 2-(diisopropylamino)propanedioate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以92%的产率得到2-(diisopropylamino)propane-1,3-diol
  参考文献：
  名称：

  Trialkylamines More Planar at Nitrogen Than Triisopropylamine in the Solid State

  摘要：

  A short synthesis of exceedingly congested amines, with insertion of a rhodium carbenoid into an N-H bond as the key step, is described. Trialkylamines such as 2-(diisopropylamino)propane-1,3-diol (8) and 2-(2,2,6,6-tetramethyl-1-piperidinyl)propane-1,3-diol (10) may be prepared easily. Examination of amines of this type by X-ray crystallography reveals nearly planar nitrogens. Indeed, they are all more planar than the nitrogen of triisopropylamine, which had long been thought to be perfectly planar, but which is in fact very slightly pyramidal. The distance (h) of the nitrogen of triisopropylamine to the plane defined by the three carbons to which it is bonded is 0.28-0.29 angstrom. In 8, by comparison, h is 0.185 angstrom. A qualitative orbital interaction explanation is proposed to rationalize the tendency of nitrogen to planarize when attached to the 1,3-dihydroxy-2-propyl group. Cyclic voltammetric measurements of nitrogen one-electron oxidation of the nearly planar trialkylamines revealed no correlation between E-1/2(ox) and degree of planarity.

  DOI：

  10.1021/jo802086h
• 作为产物：
  描述：

  2-叠氮丙二酸二甲酯 、 二异丙胺 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 作用下， 以 二氯甲烷 为溶剂， 以12 %的产率得到dimethyl 2-(diisopropylamino)propanedioate
  参考文献：
  名称：

  一般 Ir 催化的重氮丙二酸酯 N-H 插入脂肪族和芳香族胺

  摘要：

  使用 [Ir(cod)Cl] 2作为催化剂报道了受体-受体重氮丙二酸酯试剂的一般 N-H 插入反应性。可以使用多种胺，伯胺、仲胺、脂族胺和芳族胺。温和的温度、完美的底物/反应物化学计量以及良好的官能团相容性使得该过程对于胺的（后期）官能化特别有吸引力。

  DOI：

  10.1021/acs.orglett.3c03929

文献信息

• A New Route To Hindered Tertiary Amines
  作者：Minmin Yang、Xing Wang、Hui Li、Peter Livant

  DOI：10.1021/jo010583a

  日期：2001.10.1

  dimethyl diazomalonate has been found to insert into the N-H bond of sterically hindered secondary aliphatic amines to afford hindered tertiary aliphatic amines in quite satisfactory yields. For example dimethyl 2-(dicyclohexylamino)propanedioate was formed in 85% yield from dicyclohexylamine, and the severely hindered dimethyl 2-(2,2,6,6-tetramethyl-1-piperidinyl)propanedioate was formed in 38% yield

  已发现衍生自重氮丙二酸二甲酯的Rh（2）（OAc）（4）稳定的类胡萝卜素可插入空间位阻仲脂肪族胺的NH键中，从而以令人满意的产率提供受阻叔脂肪族胺。例如，由二环己基胺以85％的收率形成2-（二环己基氨基）丙二酸二甲酯，而由2形成38％收率的严重受阻的2-（2,2,6,6-四甲基-1-哌啶基）丙二酸二甲酯。 2,6,6-四甲基哌啶。发现Rh（2）（OAc）（4）-重氮丙二酸二甲酯反应也可用于芳基烷基胺和二芳基胺。在这些情况下，检测到由类胡萝卜素正式插入芳族CH键而产生的少量产物。邻位取代导致CH插入产物的产率增加。其他重氮化合物，即。
• Trialkylamines More Planar at Nitrogen Than Triisopropylamine in the Solid State
  作者：Minmin Yang、Thomas Albrecht-Schmitt、Vince Cammarata、Peter Livant、David S. Makhanu、Richard Sykora、Wei Zhu

  DOI：10.1021/jo802086h

  日期：2009.4.3

  A short synthesis of exceedingly congested amines, with insertion of a rhodium carbenoid into an N-H bond as the key step, is described. Trialkylamines such as 2-(diisopropylamino)propane-1,3-diol (8) and 2-(2,2,6,6-tetramethyl-1-piperidinyl)propane-1,3-diol (10) may be prepared easily. Examination of amines of this type by X-ray crystallography reveals nearly planar nitrogens. Indeed, they are all more planar than the nitrogen of triisopropylamine, which had long been thought to be perfectly planar, but which is in fact very slightly pyramidal. The distance (h) of the nitrogen of triisopropylamine to the plane defined by the three carbons to which it is bonded is 0.28-0.29 angstrom. In 8, by comparison, h is 0.185 angstrom. A qualitative orbital interaction explanation is proposed to rationalize the tendency of nitrogen to planarize when attached to the 1,3-dihydroxy-2-propyl group. Cyclic voltammetric measurements of nitrogen one-electron oxidation of the nearly planar trialkylamines revealed no correlation between E-1/2(ox) and degree of planarity.
• General Ir-Catalyzed N–H Insertions of Diazomalonates into Aliphatic and Aromatic Amines
  作者：Zhuang Zhong、Céline Besnard、Jérôme Lacour

  DOI：10.1021/acs.orglett.3c03929

  日期：2024.2.9

  reactivity of acceptor–acceptor diazo malonate reagents is reported using [Ir(cod)Cl]2 as catalyst. A large range of amines, primary and secondary, aliphatic and aromatic, is possible. Mild temperatures, perfect substrate/reactant stoichiometry, and good functional group compatibility render the process particularly attractive for the (late-stage) functionalization of amines.

  使用 [Ir(cod)Cl] 2作为催化剂报道了受体-受体重氮丙二酸酯试剂的一般 N-H 插入反应性。可以使用多种胺，伯胺、仲胺、脂族胺和芳族胺。温和的温度、完美的底物/反应物化学计量以及良好的官能团相容性使得该过程对于胺的（后期）官能化特别有吸引力。