2,2-dimethylocta-5(E),7-dien-1-amine | 639058-68-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2,2-dimethylocta-5(E),7-dien-1-amine
• 英文别名: (E)-2,2-dimethylocta-5,7-dien-1-amine；(5E)-2,2-dimethylocta-5,7-dien-1-amine
• CAS: 639058-68-7
• 化学式: C₁₀H₁₉N
• 分子量: 153.268
• InChiKey: DTBGZUBHSKUWJS-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2-dimethylocta-5(E),7-dien-1-amine 在 sodium tetrahydroborate 、 bis(η3-allyl-μ-chloropalladium(II)) 、 silver trifluoromethanesulfonate 、 magnesium sulfate 、 4,5-双二苯基膦-9,9-二甲基氧杂蒽 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 48.0h， 生成 (E)-N,N-dibenzyl-3-(1-(4-methoxybenzyl)-6,6-dimethylazepan-3-yl)prop-2-en-1-amine
  参考文献：
  名称：

  通过 C-N 键复分解钯催化的闭环反应快速构建饱和 N-杂环

  摘要：

  基于化学键复分解的闭环反应能够有效构建各种循环系统，这些系统受到医学和有机界的广泛关注。然而，将 CN 键复分解作为战略性基本步骤的类似反应仍然是一个悬而未决的挑战。在此，我们报告了一种新的基本金属 CN 键复分解反应的设计，该反应能够实现钯催化的氨基二烯与缩醛胺的闭环反应。该反应在温和的条件下有效进行，并表现出广泛的底物通用性和官能团兼容性，从而产生各种具有不同骨架和官能团的 5 至 16 元 N-杂环。

  DOI：

  10.1021/jacs.0c10615
• 作为产物：
  描述：

  trans-1-iodo-3,5-hexadiene 在 lithium aluminium tetrahydride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 5.25h， 生成 2,2-dimethylocta-5(E),7-dien-1-amine
  参考文献：
  名称：

  金(I)/薄荷醇协同催化对二烯进行区域选择性和对映选择性加氢胺化

  摘要：

  醇是关键：已使用双核催化剂 ( R )-DTBM-SEGPHOS实现了 1,3-二烯的区域选择性和对映选择性加氢胺化。醇类添加剂如薄荷醇可提高反应的速率和选择性，薄荷醇与阳离子金 (I) 配位以生成可参与催化的布朗斯台德酸。Mbs=对甲氧基苯磺酰基。

  DOI：

  10.1002/anie.201104076

文献信息

• Intramolecular Hydroamination/Cyclization of Conjugated Aminodienes Catalyzed by Organolanthanide Complexes. Scope, Diastereo- and Enantioselectivity, and Reaction Mechanism
  作者：Sukwon Hong、Amber M. Kawaoka、Tobin J. Marks

  DOI：10.1021/ja036266y

  日期：2003.12.1

  precatalysts for the rapid, regioselective, and highly diastereoselective intramolecular hydroamination/cyclization of primary and secondary amines tethered to conjugated dienes. The rates of aminodiene cyclizations are significantly more rapid than those of the corresponding aminoalkenes. This dienyl group rate enhancement as well as substituent group (R) effects on turnover frequencies is consistent with

  一般类型的有机镧系元素配合物 Cp'(2)LnCH(TMS)(2) (Cp' = eta(5)-Me(5)C(5); Ln = La, Sm, Y; TMS = SiMe(3) ) 和 CGCSmN(TMS)(2) (CGC = Me(2)Si(eta(5)-Me(4)C(5))((t)()BuN)) 作为快速、区域选择性的有效预催化剂，以及与共轭二烯相连的伯胺和仲胺的高度非对映选择性分子内加氢胺化/环化。氨基二烯环化的速度明显快于相应的氨基烯烃。这种二烯基速率增强以及取代基 (R) 对转换频率的影响与提议的过渡态电子需求一致。动力学和机械数据平行单取代氨基烯烃加氢胺化/环化，转换限制 C=C 插入 Ln-N 键，可能形成 Ln-eta(3) 烯丙基中间体，然后快速质子分解所得 Ln-C 键。速率定律在[催化剂]中是一级的，在[氨基二烯]中是零级的。然而，根据特定的底物和催化剂组合，与零级
• Constrained Geometry Organoactinides as Versatile Catalysts for the Intramolecular Hydroamination/Cyclization of Primary and Secondary Amines Having Diverse Tethered C−C Unsaturation
  作者：Bryan D. Stubbert、Tobin J. Marks

  DOI：10.1021/ja0665444

  日期：2007.4.1

  A series of "constrained geometry" organoactinide complexes, (CGC)An(NMe)(2) (CGC = Me2Si(eta(5)-Me4C5)((BuN)-Bu-t); An = Th, 1; U, 2), has been prepared via efficient in situ, two-step protodeamination routes in good yields and high purity. Both 1 and 2 are quantitatively converted to the neutrally charged, solvent-free dichlorides (1-Cl-2, 2-Cl-2) and slightly more soluble diiodides (1-I-2, 2-I-2) with excess Me3Si-X (X = Cl, I) in non-coordinating solvents. The new complexes were characterized by NMR spectroscopy, elemental analysis, and (for 1 and 2) single-crystal X-ray diffraction, revealing substantially increased metal coordinative unsaturation vs the corresponding Me2SiCp ''(2)AnR(2) (Cp '' = eta(5)-Me4C5; An = Th, R = CH2(SiMe3), 3; An = U, R = CH2Ph, 4) and Cp'(2)AnR(2) (Cp' = eta(5)-Me5C5 ; An = Th, R = CH2(SiMe3), 5; An = U, R = CH2(SiMe3), 6) complexes. Complexes 1-6 exhibit broad applicability for the intramolecular hydroamination of diverse C-C unsaturations, including terminal and internal aminoalkenes (primary and secondary amines), aminoalkynes (primary and secondary amines), aminoallenes, and aminodienes. Large turnover frequencies (N-t up to 3000 h(-1)) and high regioselectivities (>= 95%) are observed throughout, along with moderate to high diastereoselectivities (up to 90% trans ring closures). With several noteworthy exceptions, reactivity trends track relative 5f ionic radii and ancillary ligand coordinative unsaturation. Reactivity patterns and activation parameters are consistent with a reaction pathway proceeding via turnover-limiting CC/CC insertion into the An-N sigma-bond.
• A Carbaboranylmercuric Salt Catalyzed Reaction; Highly Regioselective Cycloisomerization of 1,3-Dienes
  作者：Hirofumi Yamamoto、Ikuo Sasaki、Shinya Shiomi、Naoto Yamasaki、Hiroshi Imagawa

  DOI：10.1021/ol300678r

  日期：2012.5.4

  The combination of carbaboranylmercuric chloride (new type of bulky Lewis acid) and silver triflate efficiently catalyzes cycloisomerization of 1, 3-dienes at room temperature. The catalytic system gives allyl-substituted azacycles and cycloalkanes in excellent yields with high to complete regioselectivity.
• Palladium-Catalyzed Ring-Closing Reaction via C–N Bond Metathesis for Rapid Construction of Saturated <i>N</i>-Heterocycles
  作者：Bangkui Yu、Suchen Zou、Hongchi Liu、Hanmin Huang

  DOI：10.1021/jacs.0c10615

  日期：2020.10.28

  The ring-closing reactions based on chemical bond metathesis enable the efficient construction of a wide variety of cyclic systems which receive broad interest from medicinal and organic communities. However, the analogous reaction with C-N bond metathesis as a strategic fundamental step remains an unanswered challenge. Herein, we report the design of a new fundamental metallic C-N bond metathesis reaction

  基于化学键复分解的闭环反应能够有效构建各种循环系统，这些系统受到医学和有机界的广泛关注。然而，将 CN 键复分解作为战略性基本步骤的类似反应仍然是一个悬而未决的挑战。在此，我们报告了一种新的基本金属 CN 键复分解反应的设计，该反应能够实现钯催化的氨基二烯与缩醛胺的闭环反应。该反应在温和的条件下有效进行，并表现出广泛的底物通用性和官能团兼容性，从而产生各种具有不同骨架和官能团的 5 至 16 元 N-杂环。
• Regio- and Enantioselective Hydroamination of Dienes by Gold(I)/Menthol Cooperative Catalysis
  作者：Osamu Kanno、Wataru Kuriyama、Z. Jane Wang、F. Dean Toste

  DOI：10.1002/anie.201104076

  日期：2011.10.10

  Alcohol is key: Regio‐ and enantioselective hydroamination of 1,3‐dienes has been achieved with the dinuclear catalyst (R)‐DTBM‐SEGPHOS. The rate and selectivity of the reaction are enhanced by alcohol additives like menthol, which coordinates the cationic gold(I) to generate a Brønsted acid that can participate in catalysis. Mbs=p‐methoxybenzenesulfonyl.

  醇是关键：已使用双核催化剂 ( R )-DTBM-SEGPHOS实现了 1,3-二烯的区域选择性和对映选择性加氢胺化。醇类添加剂如薄荷醇可提高反应的速率和选择性，薄荷醇与阳离子金 (I) 配位以生成可参与催化的布朗斯台德酸。Mbs=对甲氧基苯磺酰基。