1-D-cyclohexene | 42843-17-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1-D-cyclohexene
• 英文别名: 1-deuterio-cyclohexene；Cyclohexene-d1；1-deuteriocyclohexene
• CAS: 42843-17-4
• 化学式: C₆H₁₀
• 分子量: 83.1375
• InChiKey: HGCIXCUEYOPUTN-MICDWDOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  1-D-cyclohexene 、 [N-(nosyl)imino]phenyliodinane 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 为溶剂， 生成 N-(2-deuteriocyclohex-2-en-1-yl)-4-nitrobenzenesulfonamide 、 N-(3-deuteriocyclohex-2-en-1-yl)-4-nitrobenzenesulfonamide
  参考文献：
  名称：

  Rhodium(II)-catalyzed aziridinations and CH insertions with [N-(p-nitrobenzenesulfonyl)imino]phenyliodinane

  摘要：

  The [Rh-2(OAc)(4)]-catalyzed decomposition of NsN=IPh {[N-(p-nitrobenzenesulfonyl)imino]phenyliodinane} in the presence of olefins affords aziridines in yields of up to 85%. The aziridination of cis-hex-2-ene and cis-beta- methylstyrene is stereospecific, but, cis-stilbene affords a 3:1 mixture of cis- and trans-aziridines in low yield. With chiral Rh(II) catalysts, optically active aziridines are formed having enantiomeric excesses of up to 73%. The NsN=IPh-[Rh-2(OAc)(4)] system is also efficient for the allylic amination of olefins and for insertion into CH bonds, activated by phenyl or oxygen substituents.

  DOI：

  10.1002/(sici)1099-1395(199606)9:6<341::aid-poc791>3.0.co;2-5
• 作为产物：
  描述：

  1-deuteriocyclohex-2-en-1-ol 在 四丙基溴化铵 作用下， 以 吡啶 、 N,N-二甲基甲酰胺 为溶剂， 反应 36.0h， 生成 1-D-cyclohexene
  参考文献：
  名称：

  Hoffmann, Joachim; Holst, Hartmut; Volz, Wolfgang, Journal of Chemical Research, Miniprint, 1989, # 2, p. 401 - 428

  摘要：

  DOI：

文献信息

• Catalytic Allylic C−H Acetoxylation and Benzoyloxylation via Suggested (η³-Allyl)palladium(IV) Intermediates
  作者：Lukasz T. Pilarski、Nicklas Selander、Dietrich Böse、Kálmán J. Szabó

  DOI：10.1021/ol9023369

  日期：2009.12.3

  Palladium-catalyzed allylic acetoxylations and benzoyloxylations were carried out using iodonium salts. The reactions proceed under mild conditions with high regio- and stereoselectivity. The catalysis can be performed under both acidic and nonacidic conditions without use of BQ or other external oxidants and activator ligands. Deuterium labeling experiments clearly show that the catalytic reaction

  使用碘鎓盐进行钯催化的烯丙基乙酰氧基化和苯甲酰氧基化。反应在温和条件下以高区域选择性和立体选择性进行。该催化反应可以在酸性和非酸性条件下进行，而无需使用BQ或其他外部氧化剂和活化剂配体。氘标记实验清楚地表明，通过（η催化反应进行3 -烯丙基）钯中间体。用一种催化剂进行的化学计量研究为形成Pd（IV）物种提供了证据。
• Rhodium(II)-Catalyzed CH Insertions with {[(4-Nitrophenyl)sulfonyl]imino}phenyl-λ³-iodane
  作者：Ivo Nägeli、Corine Baud、GéErald Bernardinelli、Yvan Jacquier、Mary Moraon、Paul Müllet

  DOI：10.1002/hlca.19970800407

  日期：1997.6.30

  in formal insertions into CH bonds, activated by phenyl or vinyl groups, or by O-substituents. Scope and limitations of the reaction were investigated. Yields of up to 84% were achieved in the most favorable cases. Yields were enhanced by electron-releasing substituents and decreased by steric hindrance. Aziridination competed with allylic insertion with olefinic substrates. The insertion reaction proceeded

  所述的[Rh 2（OAc）4 ]的催化的分解[（4-硝基苯基）磺酰基]亚氨基}苯基-λ 3 -iodane（NsNIPh）导致正式插入到CH键，被苯基或乙烯基活化，或通过O-取代基。研究了反应的范围和局限性。在最有利的情况下，产率高达84％。释放电子的取代基提高了产率，而空间位阻降低了产率。叠氮化与烯烃底物的烯丙基插入竞争。插入反应在保持构型的情况下进行。使用手性Rh II催化剂，观察到适度的不对称诱导。提出了一种机制，涉及通过Rh络合的腈直接插入CH键。
• Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase
  作者：Feng Chen、Manish Shetty、Meng Wang、Hui Shi、Yuanshuai Liu、Donald M. Camaioni、Oliver Y. Gutiérrez、Johannes A. Lercher

  DOI：10.1021/acscatal.0c05674

  日期：2021.3.5

  The rate of acid–base-catalyzed dehydration of alcohols strongly depends on the solvent and the environment of the acid sites. We find that Brønsted acidic sites in large-pore zeolites, but not in medium-pore zeolites, catalyze cyclohexanol dehydration in decalin at significantly higher rates than hydrated hydronium ions in aqueous phase. Specifically, the difference in turnover rates between the two

  酸碱催化的醇类脱水速率在很大程度上取决于溶剂和酸性部位的环境。我们发现大孔沸石中的布朗斯台德酸性位点，而不是中孔沸石中的布朗斯台德酸位点，催化萘烷中环己醇的脱水速率明显高于水相中水合氢离子。具体来说，两种溶剂之间的周转率差异在H-BEA和H-FAU上达2-3个数量级，而对于H-MFI则非常小（在2倍之内）。结合动力学，同位素示踪剂和21 H NMR测量表明，环己醇的脱水通常遵循十氢化萘中的E 1消除途径。一个显着的例外是H-MFI上的单体脱水路线，该路线表现出低得多的活化能和基本上为负的活化熵，这似乎与E2型机理有关。C–O键断裂在十氢化萘中显示出主要的速率控制程度，这与去质子化（CH裂解）在水相脱水中的速率限制相反。
• Functionalization of Unactivated Alkenes through Iridium-Catalyzed Borylation of Carbon−Hydrogen Bonds. Mechanism and Synthetic Applications
  作者：Vilhelm J. Olsson、Kálmán J. Szabó

  DOI：10.1021/jo9014694

  日期：2009.10.16

  methylimidazole and DBU, the iridium-catalyzed borylation led to formation of allyl boronates, which reacted with aldehydes in a one-pot sequence affording stereodefined homoallylic alcohols. Cycloalkenes without additives as well as acyclic substrates gave vinylic boronates, which were coupled with organohalides in a Suzuki−Miyaura sequence. By this process allylic and vinylic silabutadiene derivatives

  本文介绍了一种有效的碳-碳键形成反应，该反应基于未活化烯烃的碳-氢键官能化。此过程基于铱催化烯烃的硼化反应，然后进行碳-碳键形成反应，从而原位生成烯丙基和乙烯基硼酸酯。对于环烯烃，可以有效地控制碳氢键官能化的选择性。通过使用添加剂，例如甲基咪唑和DBU，铱催化的硼酸酯化反应会生成烯丙基硼酸酯，后者与醛按一锅法反应生成立体定义的均烯丙基醇。没有添加剂以及无环底物的环烯烃会生成乙烯基硼酸酯，并以Suzuki-Miyaura序列与有机卤化物偶联。通过该方法，可以从烯丙基硅烷制备具有优异的区域选择性和立体选择性的烯丙基和乙烯基的硅丁二烯衍生物。通过同位素标记实验，测量动力学同位素效应以及研究添加剂对工艺选择性的影响，探索了基于硼化反应的碳氢键官能化机理。可以得出结论，该反应是通过脱氢硼化反应机理进行的，该机理显示出与钯催化的Heck偶联反应相似的特征。测量动力学同位素效应并研究添加剂对工艺选择性的
• Photochemistry of alkyl halides. 11. Competing reaction via carbene and carbocationic intermediates
  作者：Paul J. Kropp、Joy A. Sawyer、John J. Snyder

  DOI：10.1021/jo00183a019

  日期：1984.5