(1R,2R)-N1,N1-二丙基环己烷-1,2-二胺 | 860994-91-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: (1R,2R)-N1,N1-二丙基环己烷-1,2-二胺
• 英文名称: (1R,2R)-N1,N1-dipropylcyclohexane-1,2-diamine
• 英文别名: (1R,2R)-N,N-dipropylcyclohexane-1,2-diamine；(R,R)-N,N-dipropylcyclohexane-1,2-diamine；(1R,2R)-2-(dipropylamino)cyclohexanamine；(1R,2R)-2-N,2-N-dipropylcyclohexane-1,2-diamine
• CAS: 860994-91-8
• 化学式: C₁₂H₂₆N₂
• 分子量: 198.352
• InChiKey: ZMRBYUCFPRTGMI-VXGBXAGGSA-N

物化性质

• 沸点：
  250.4±8.0 °C(Predicted)
• 密度：
  0.90±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2R)-N1,N1-二丙基环己烷-1,2-二胺 、 硫光气 在 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 反应 0.42h， 以77%的产率得到(1R,2R)-2-isothiocyanato-N,N-dipropylcyclohexanamine
  参考文献：
  名称：

  Cooperative Catalysis by Tertiary Amino-Thioureas:  Mechanism and Basis for Enantioselectivity of Ketone Cyanosilylation

  摘要：

  The mechanism of the enantioselective cyanosilylation of ketones catalyzed by tertiary aminothiourea derivatives was investigated using a combination of experimental and theoretical methods. The kinetic analysis is consistent with a cooperative mechanism in which both the thiourea and the tertiary amine of the catalyst are involved productively in the rate-limiting cyanide addition step. Density functional theory calculations were used to distinguish between mechanisms involving thiourea activation of ketone or of cyanide in the enantioselectivity-determining step. The strong correlation obtained between experimental and calculated ee's for a range of substrates and catalysts provides support for the most favorable calculated transition structures involving amine-bound HCN adding to thiourea-bound ketone. The calculations suggest that enantioselectivity arises from direct interactions between the ketone substrate and the amino-acid derived portion of the catalyst. On the basis of this insight, more enantioselective catalysts with broader substrate scope were prepared and evaluated experimentally.

  DOI：

  10.1021/ja0735352
• 作为产物：
  描述：

  N-((1R,2R)-2-aminocyclohexyl)benzamide 在 盐酸 、 水 作用下， 以 水 、 乙腈 为溶剂， 反应 0.25h， 生成 (1R,2R)-N1,N1-二丙基环己烷-1,2-二胺
  参考文献：
  名称：

  用于不对称催化的仿生鸟嘌呤基有机催化剂的设计与开发

  摘要：

  介绍了一系列新型有机催化剂的设计、制备和研究。催化剂的设计灵感来自于 DNA 核碱基发展精确和明确的氢键的能力。我们已经表明，这种现象可用于创建一种有用的有机催化剂，该催化剂显示出类似于常见有机底物的识别模式。基于鸟嘌呤结构的选定双功能催化剂已被证明可催化 1,3-二羰基化合物与各种硝基烯烃的共轭加成，从而以良好的产率和对映选择性提供产品。

  DOI：

  10.1002/ejoc.201200118
• 作为试剂：
  描述：

  1-乙烯基-2,4-二硝基苯 在 (1R,2R)-N1,N1-二丙基环己烷-1,2-二胺 、 溶剂黄146 、 苯甲酸 、 三氟乙酸 作用下， 以 乙醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 172.0h， 生成 (R)-3a-(2,4-dinitrophenethyl)-2-phenyl-4,5,6,7-tetrahydro-2H-indazol-3(3aH)-one
  参考文献：
  名称：

  Construction of an all-carbon quaternary stereocenter by organocatalytic enantioselective α-functionalization of α-substituted β-ketocarbonyls with electron deficient vinylarenes

  摘要：

  通过手性胺催化的选择性α-官能化方法，有效地构建了全碳季碳立体中心，该方法使用了α-取代的β-酮羰基化合物和电亏电子的乙烯芳烃。

  DOI：

  10.1039/c5cc03562g

文献信息

• A Simple Primary−Tertiary Diamine−Brønsted Acid Catalyst for Asymmetric Direct Aldol Reactions of Linear Aliphatic Ketones
  作者：Sanzhong Luo、Hui Xu、Jiuyuan Li、Long Zhang、Jin-Pei Cheng

  DOI：10.1021/ja069372j

  日期：2007.3.1

  regio- and diastereoselectivity and enantioselectivity under ambient temperature. Significantly, the reactions accommodate the synthetically important but challenging substrates, such as linear aliphatic ketones, with high regioselectivity and unprecedented syn diastereoselectivity. These results are in sharp contrast with the secondary amine mediated similar reactions wherein anti diastereoselectivity

  与已充分探索的带有仲胺的烯胺催化相比，开发高效的基于烯胺的伯胺催化剂直到最近仍然是一个难以捉摸的目标。我们在本文中提出了一种简单的手性伯-叔二胺 1d 与 TfOH 结合用作有效的基于烯胺的伯胺催化剂。1d-TfOH催化体系可以有效催化不对称直接醛醇反应，底物范围广，在环境温度下具有高区域选择性和非对映选择性以及对映选择性。值得注意的是，这些反应适应了合成上重要但具有挑战性的底物，例如线性脂肪族酮，具有高区域选择性和前所未有的顺式非对映选择性。
• Directing the Activation of Donor-Acceptor Cyclopropanes Towards Stereoselective 1,3-Dipolar Cycloaddition Reactions by Brønsted Base Catalysis
  作者：Jakob Blom、Andreu Vidal-Albalat、Julie Jørgensen、Casper L. Barløse、Kamilla S. Jessen、Marc V. Iversen、Karl Anker Jørgensen

  DOI：10.1002/anie.201706150

  日期：2017.9.18

  first stereoselective organocatalyzed [3+2] cycloaddition reaction of donor-acceptor cyclopropanes is presented. By using an optically active bifunctional Brønsted base catalyst, racemic di-cyano cyclopropylketones can be activated to undergo a stereoselective 1,3-dipolar reaction with mono- and polysubstituted nitroolefins. The reaction affords functionalized cyclopentanes with three contiguous stereocenters

  极性末端：介绍了供体-受体环丙烷的第一个立体选择性有机催化的[3 + 2]环加成反应。通过使用旋光性双官能布朗斯台德碱催化剂，外消旋二氰基环丙基酮可以被活化，从而与单或多取代的硝基烯烃发生立体选择性的1,3-偶极反应。该反应以高产率和立体选择性提供具有三个连续的立体中心的官能化的环戊烷。
• Enantioselective aldol reaction of cyclic ketones with aryl aldehydes catalyzed by a cyclohexanediamine derived salt in the presence of water
  作者：Jin-Hong Lin、Cheng-Pan Zhang、Ji-Chang Xiao

  DOI：10.1039/b916583e

  日期：——

  Water was found to be a suitable reaction medium for the direct asymmetric aldol reaction of various cyclic ketones with aryl aldehydes catalyzed by a primary-tertiary diamine-Brønsted acid.

  水 被发现是一种适合各种直接不对称醛醇缩合反应的反应介质 环酮 伯叔二胺-布朗斯台德酸催化的芳基醛
• Thiourea-Catalyzed Enantioselective Cyanosilylation of Ketones
  作者：Douglas E. Fuerst、Eric N. Jacobsen

  DOI：10.1021/ja052511x

  日期：2005.6.1

  The new chiral amino thiourea catalyst 3d promotes the highly enantioselective cyanosilylation of a wide variety of ketones. The hindered tertiary amine substituent plays a crucial role with regard to both stereoinduction and reactivity, suggesting a cooperative mechanism involving electrophile activation by thiourea and nucleophile activation by the amine.
• Cooperative Catalysis by Tertiary Amino-Thioureas:  Mechanism and Basis for Enantioselectivity of Ketone Cyanosilylation
  作者：Stephan J. Zuend、Eric N. Jacobsen

  DOI：10.1021/ja0735352

  日期：2007.12.1

  The mechanism of the enantioselective cyanosilylation of ketones catalyzed by tertiary aminothiourea derivatives was investigated using a combination of experimental and theoretical methods. The kinetic analysis is consistent with a cooperative mechanism in which both the thiourea and the tertiary amine of the catalyst are involved productively in the rate-limiting cyanide addition step. Density functional theory calculations were used to distinguish between mechanisms involving thiourea activation of ketone or of cyanide in the enantioselectivity-determining step. The strong correlation obtained between experimental and calculated ee's for a range of substrates and catalysts provides support for the most favorable calculated transition structures involving amine-bound HCN adding to thiourea-bound ketone. The calculations suggest that enantioselectivity arises from direct interactions between the ketone substrate and the amino-acid derived portion of the catalyst. On the basis of this insight, more enantioselective catalysts with broader substrate scope were prepared and evaluated experimentally.