2-deuterio-indene | 50613-68-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 2-deuterio-indene
• 英文别名: 2-deuterio-1H-indene
• CAS: 50613-68-8
• 化学式: C₉H₈
• 分子量: 117.155
• InChiKey: YBYIRNPNPLQARY-WFVSFCRTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-deuterio-indene 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 水 、 二甲基亚砜 为溶剂， 反应 6.0h， 以95%的产率得到trans-2-bromo-2-d-indanol
  参考文献：
  名称：

  Enantioselective Synthesis of cis- and trans-2(S)-Amino-1-d-indane:  Debrominative [1,2]-Hydride Shift Rearrangement by Reduction of cis-2-Azido-1-bromoindane with LiAlD₄

  摘要：

  This article describes the synthesis of the racemic and optically pure forms of (1R,2S)-cis- and (1S,2S)-trans-2-Amino-1-d-indanes 2 {94% ee} and 3 {83% ee} (ee determined by H-2 NMR in chiral liquid crystal PBLG/CH2Cl2, Courtieu, J. et al. J. Am. Chem. Soc. 1995, 117, 6520) prepared by LiAlD4 reduction of (+/-)- and (1S,2S)-trans-2-azido-1-bromomoindane (11) {87% ee} and (+/-) and (1R,2S)-cis-2-azido-1-[(methanesulfonyl)oxy]indane (10) {83% ee}, respectively. Whereas the LiAlD4 reduction of trans-2-azido-1-bromomoindane (11) led to cis-2-amino-1-d-indane 2 by a S(N)2 pathway, exclusively, the reduction of cis-1-bromo derivative 12 gave only small amounts of the S(N)2 product trans-2-amino-1-d-indane (3) (15%) accompanied by 2-amino-2-d-indane (4) (85%) in which the deuterium atom is incorporated in alpha position to the amino group. It was established that the primary amine 4 comes from a stereospecific [1,2]-hydride shift rearrangement, We propose that the azido group is reduced first, and the [1,2]-hydride shift rearrangement prevails over the competitive S(N)2 substitution. The exclusive formation of trans-2-amino-1-d-indane (3) requires cis-2-azido-1-[(methanesulfonyl)oxy]indane (10) where the mesylate assisted by electrophilic Li+ cation switches the deuteride attack to the ester carbon and the direct S(N)2 substitution occurs before the azide is reduced.

  DOI：

  10.1021/jo970378o
• 作为产物：
  描述：

  2-茚酮 在 lithium aluminium deuteride 、 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 78.75h， 生成 2-deuterio-indene
  参考文献：
  名称：

  Enantioselective Synthesis of cis- and trans-2(S)-Amino-1-d-indane:  Debrominative [1,2]-Hydride Shift Rearrangement by Reduction of cis-2-Azido-1-bromoindane with LiAlD₄

  摘要：

  This article describes the synthesis of the racemic and optically pure forms of (1R,2S)-cis- and (1S,2S)-trans-2-Amino-1-d-indanes 2 {94% ee} and 3 {83% ee} (ee determined by H-2 NMR in chiral liquid crystal PBLG/CH2Cl2, Courtieu, J. et al. J. Am. Chem. Soc. 1995, 117, 6520) prepared by LiAlD4 reduction of (+/-)- and (1S,2S)-trans-2-azido-1-bromomoindane (11) {87% ee} and (+/-) and (1R,2S)-cis-2-azido-1-[(methanesulfonyl)oxy]indane (10) {83% ee}, respectively. Whereas the LiAlD4 reduction of trans-2-azido-1-bromomoindane (11) led to cis-2-amino-1-d-indane 2 by a S(N)2 pathway, exclusively, the reduction of cis-1-bromo derivative 12 gave only small amounts of the S(N)2 product trans-2-amino-1-d-indane (3) (15%) accompanied by 2-amino-2-d-indane (4) (85%) in which the deuterium atom is incorporated in alpha position to the amino group. It was established that the primary amine 4 comes from a stereospecific [1,2]-hydride shift rearrangement, We propose that the azido group is reduced first, and the [1,2]-hydride shift rearrangement prevails over the competitive S(N)2 substitution. The exclusive formation of trans-2-amino-1-d-indane (3) requires cis-2-azido-1-[(methanesulfonyl)oxy]indane (10) where the mesylate assisted by electrophilic Li+ cation switches the deuteride attack to the ester carbon and the direct S(N)2 substitution occurs before the azide is reduced.

  DOI：

  10.1021/jo970378o

文献信息

• Selective Catalytic C–H Alkylation of Alkenes with Alcohols
  作者：Dong-Hwan Lee、Ki-Hyeok Kwon、Chae S. Yi

  DOI：10.1126/science.1208839

  日期：2011.9.16

  A ruthenium catalyst forms carbon-carbon bonds between olefins and alcohols while liberating only water as a by-product. Alkenes and alcohols are among the most abundant and commonly used organic feedstock in industrial processes. We report a selective catalytic alkylation reaction of alkenes with alcohols that forms a carbon-carbon bond between vinyl carbon-hydrogen (C–H) and carbon-hydroxy centers

  钌催化剂在烯烃和醇之间形成碳-碳键，同时仅释放水作为副产物。烯烃和醇是工业过程中最丰富和最常用的有机原料。我们报告了烯烃与醇的选择性催化烷基化反应，该反应在乙烯基碳氢（C-H）和碳-羟基中心之间形成碳-碳键，同时失去水。阳离子钌络合物 [(C6H6)(PCy3)(CO)RuH]+BF4–（Cy，环己基）可在 75°C 至 110°C 的温度范围内在 2 至 8 小时内催化溶液中的烷基化，并耐受广泛的底物官能团，包括胺和羰基。初步的机理研究与醇的 Friedel-Crafts 型亲电活化不一致，
• The reactions of flavin analogues and other heterocycles as models for bacterial bioluminescence
  作者：F. McCapra、P.D. Leeson、V. Donovan、G. Perry

  DOI：10.1016/s0040-4020(01)87387-7

  日期：1986.1

  The reactions of 10a-peroxyflavins have been examined to increase understanding of the oxidative and chemiluminescent reactions catalysed by the flavin co-enzymes. A remarkable series of structural requirements in the peroxides used has been uncovered, and in addition to serving as models for the mechanism of bacterial luciferase, they constitute a set of new chemiluminescent reactions.

  已检查了10a-过氧黄素的反应，以加深对黄素辅酶催化的氧化和化学发光反应的了解。已经发现了所用过氧化物中一系列显着的结构要求，并且除了充当细菌荧光素酶机理的模型外，它们还构成了一组新的化学发光反应。
• Approaches to pseudoindene
  作者：Margaret.A. O'leary、Dieter Wege

  DOI：10.1016/s0040-4020(01)97701-4

  日期：1981.1

  The title carbenes, which in principle can all serve as precursors to the reactive hydrocarbon pseudoindene, have been generated by the photolysis of the sodium salts of the tosylhydrazones of (a) benzocyclobutene-1-carboxaldehyde, (b) 2-methylbenzocyclobutenone and (c) o-formylstyrene. Indene was formed in reactions (a) and (c): in the former case deuterium labelling experiments suggest a ring expansion

  标题碳酰苯原则上可以全部用作反应性烃假茚的前体，是通过光解（a）苯并环丁烯-1-羧醛，（b）2-甲基苯并环丁烯酮和（c ）o-甲酰基苯乙烯。茚在反应（a）和（c）中形成：在前一种情况下，氘标记实验表明是扩环机理，而不是假茚满中间体。在后一种情况下，氘标记和捕集实验涉及对称的异茚中间体，该中间体可以通过假茚或邻苯乙烯基卡宾的直接电环闭合而产生。
• Ruthenium Dihydrogen Complex for C–H Activation: Catalytic H/D Exchange under Mild Conditions
  作者：Martin H. G. Prechtl、Markus Hölscher、Yehoshoa Ben‐David、Nils Theyssen、David Milstein、Walter Leitner

  DOI：10.1002/ejic.200800359

  日期：2008.8

  Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp)(η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25–75 °C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A preference for protons at sp2 carbons was observed with conversions up to >90 % and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed

  用 [Ru(dtbpmp)(η2-H2)(H)2] (1) 作为催化剂研究了催化 H/D 交换反应。在温和的反应条件 (25–75 °C) 下，范围广泛的芳烃和烯烃与 [D6] 苯进行 H/D 交换。在某些情况下，转化率高达 >90% 和显着的区域选择性，观察到对 sp2 碳的质子偏爱。为了获得更多的反应见解，以萘为底物进行了基于 NMR 的动力学研究，揭示了 15.8 kcal mol-1 的 β 位 H/D 交换的活化能。此外，通过模型配合物（PMe2 供体位点）和实际催化剂（PtBu2 供体位点）的 DFT 计算研究了反应机理的关键步骤。计算得出 Gibb 的自由活化能在 10–16 kcal mol–1 范围内，
• Hydroalkenylation of Alkynes Catalyzed by Dinuclear Palladium Complexes via C–H Bond Activation
  作者：Naofumi Tsukada、Hiroyuki Setoguchi、Tomohiro Mitsuboshi、Yoshio Inoue

  DOI：10.1246/cl.2006.1164

  日期：2006.10

  Hydroalkenylation of alkynes with alkenes proceeded in the presence of dinuclear palladium complexes and lithium tri-tert-butoxyaluminum hydride to yield 1,3-dienes.

  在双核钯配合物和三叔丁氧基氢化铝锂存在下，炔烃与烯烃进行加氢烯基化，生成 1,3-二烯。