(2-cyclododecylidenevinyl)trimethylsilane | 1266615-06-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (2-cyclododecylidenevinyl)trimethylsilane
• CAS: 1266615-06-8
• 化学式: C₁₇H₃₂Si
• 分子量: 264.527
• InChiKey: DOGSJXLAQYSZHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.25
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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-cyclododecylidenevinyl)trimethylsilane 在 iron(II) chloride tetrahydrate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 乙腈 为溶剂， 反应 8.0h， 以75%的产率得到2-(cyclododecen-1-yl)ethynyl-trimethylsilane
  参考文献：
  名称：

  铁（II）催化的不同氧化剂对丙二烯的氧化转化

  摘要：

  描述了丙二烯的取代基和氧化剂依赖性转化。考虑到取代基对丙二烯反应性的深远影响，当与不同的亲电试剂/氧化剂反应时，丙二烯结构的细微差异体现在各种产物的形成中。通常，非甲硅烷基化的丙二烯的反应通过与杂化的C2形成DD键（2,3-二氯-5,6-二氰基对苯醌）或TBHP（通过在杂化C2上形成C-O键）来涉及烯丙基阳离子中间体。叔丁基过氧化氢）中，用的FeCl沿2 ⋅4ħ 2O（10摩尔％）。相反，甲硅烷基化丙二烯青睐炔阳离子中间体的由丙二烯氢化物转移到氧化剂，从而产生1,3-烯炔（E1产品）或丙炔醚THBP（S形成Ñ 1个产物）。DFT计算强烈支持由非甲硅烷基化和甲硅烷基化的丙二烯形成这些不同的假定阳离子中间体。

  DOI：

  10.1002/anie.201510006
• 作为产物：
  描述：

  环十二酮 、 三甲基硅烷化重氮甲烷 在 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 2.5h， 以63%的产率得到(2-cyclododecylidenevinyl)trimethylsilane
  参考文献：
  名称：

  Selectivity Control in Alkylidene Carbene-Mediated C−H Insertion and Allene Formation

  摘要：

  Regioselectivity of alkylidene carbene-mediated C-H insertion was explored utilizing electronic, conformational, steric, and stereoelectronic effects. Relying on these factors, highly regio- and chemoselective carbene insertion reaction of C-H bonds in different environments could be obtained. The observed selectivity clearly indicates that an electronic effect plays a more important role than steric effect. In general, C-H bonds in conformationally rigid cyclic environments are less reactive than those in acyclic systems toward carbene insertion, and in this situation, a competing intermolecular reaction between alkylidene carbene and trimethylsilyldiazomethane led to the formation of allenylsilanes. The formation of allenylsilane becomes more favorable as the concentration of reaction becomes higher, as well as the C-H bonds undergoing insertion becomes electronically and conformationally deactivated.

  DOI：

  10.1021/jo102180f

文献信息

• Transformation of Carbonyl Compounds into Homologous Alkynes under Neutral Conditions: Fragmentation of Tetrazoles Derived from Cyanophosphates
  作者：Hiroki Yoneyama、Masahiro Numata、Kenji Uemura、Yoshihide Usami、Shinya Harusawa

  DOI：10.1021/acs.joc.7b00346

  日期：2017.6.2

  Cyanophosphates (CPs) can be easily prepared from either ketones or aldehydes, and their reaction with NaN3–Et3N·HCl results in the formation of azidotetrazoles. Under microwave irradiation, successive fragmentation of the azidotetrazoles generates alkylidene carbenes that undergo [1,2]-rearrangement and are transformed into homologous alkynes. Treatment of ketone-derived CPs with TMSN3 and Bu2SnO

  氰基磷酸盐（CPs）可以很容易地从酮或醛中制备，它们与NaN 3 -Et 3 N·HCl的反应导致叠氮四唑的形成。在微波辐射下，叠氮四唑的连续断裂产生亚烷基卡宾，经过[1,2]重排并转化为同源炔烃。用TMSN 3和Bu 2 SnO作为催化剂在甲苯中回流处理酮衍生的CP，可直接产生相应的内部炔烃，而醛衍生的CP与NaN 3 -Et 3 N·HCl在THF中的回流或TMSN 3反应–Bu 2回流中的甲苯中的SnO（催化）可提供高收率的同源末端炔烃。这些反应在中性条件下进行，可以成功地扩展以得到通常需要通过碱性条件的Ohira–Bestmann或Shioiri方法从相应的羰基化合物无法获得的炔烃。
• Oxidative Dimerization of Silylallenes via Activation of the Allenic C(<i>sp</i>²)–H Bond Catalyzed by Copper(I) Chloride and <i>N</i>-Hydroxyphthalimide
  作者：Venkata R. Sabbasani、Daesung Lee

  DOI：10.1021/acs.orglett.5b02433

  日期：2015.10.2

  Novel oxidative dimerization of silylallenes is described. Treatment of silylallenes with a catalytic amount of copper(I) chloride, a substoichiometric amount of N-hydroxyphthalamide, and a stoichiometric amount of a terminal oxidant diacetoxyiodobenzene afforded head-to-head dimers as the main products. Silyallenes containing a small ring afforded only dimers, whereas as the ring size increased 1

  描述了甲硅烷基亚烷基的新型氧化二聚作用。用催化量的氯化铜（I），亚化学计量量的N-羟基邻苯二甲酰胺和化学计量量的末端氧化剂二乙酰氧基碘苯处理甲硅烷基烯以头对头二聚体为主要产物。含有小环的硅丙二烯只能提供二聚体，而随着环尺寸的增加，1,3-烯炔成为更有利的产物。对于含有无环取代基的甲硅烷基亚烷基而言，二聚体形成是常态，其中N-羟基邻苯二甲酰亚胺在炔丙基中心反应生成相应的氨氧基醚。
• Accessing Z‐Enynes via Cobalt‐Catalyzed Propargylic Dehydrogenation
  作者：Alexandra K. Bodnar、Timothy R. Newhouse

  DOI：10.1002/anie.202402638

  日期：——

  Alkenes constitute an enabling motif in organic synthesis, as they can be functionalized to form highly substituted molecules. Z‐alkenes are generally challenging to access due to the thermodynamic preference for the formation of E‐alkenes compared to Z‐alkenes. Dehydrogenation methodologies to selectively form Z‐alkenes have not yet been reported. Herein, we report a Z‐selective, propargylic dehydrogenation that provides 1,3‐enynes through the invention of a Co‐catalyzed oxidation system. Observation of a kinetic isotope effect (KIE) revealed that deprotonation of the propargylic position is the rate limiting step. Additionally, isomerization experiments were conducted and confirmed that the observed Z‐selectivity is a kinetic effect. A proposed stereomechanistic model for the Z‐selectivity is included.
• Complementary Iron(II)‐Catalyzed Oxidative Transformations of Allenes with Different Oxidants
  作者：Venkata R. Sabbasani、Hyunjin Lee、Yuanzhi Xia、Daesung Lee

  DOI：10.1002/anie.201510006

  日期：2016.1.18

  Substituent‐ and oxidant‐dependent transformations of allenes are described. Given the profound influence of the substituent on the reactivity of allenes, the subtle differences in allene structures are manifested in the formation of diverse products when reacted with different electrophiles/oxidants. In general, reactions of nonsilylated allenes involve an allylic cation intermediate by forming a

  描述了丙二烯的取代基和氧化剂依赖性转化。考虑到取代基对丙二烯反应性的深远影响，当与不同的亲电试剂/氧化剂反应时，丙二烯结构的细微差异体现在各种产物的形成中。通常，非甲硅烷基化的丙二烯的反应通过与杂化的C2形成DD键（2,3-二氯-5,6-二氰基对苯醌）或TBHP（通过在杂化C2上形成C-O键）来涉及烯丙基阳离子中间体。叔丁基过氧化氢）中，用的FeCl沿2 ⋅4ħ 2O（10摩尔％）。相反，甲硅烷基化丙二烯青睐炔阳离子中间体的由丙二烯氢化物转移到氧化剂，从而产生1,3-烯炔（E1产品）或丙炔醚THBP（S形成Ñ 1个产物）。DFT计算强烈支持由非甲硅烷基化和甲硅烷基化的丙二烯形成这些不同的假定阳离子中间体。
• Selectivity Control in Alkylidene Carbene-Mediated C−H Insertion and Allene Formation
  作者：Jun-Cheng Zheng、Sang Young Yun、Chunrui Sun、Nam-Kyu Lee、Daesung Lee

  DOI：10.1021/jo102180f

  日期：2011.2.18

  Regioselectivity of alkylidene carbene-mediated C-H insertion was explored utilizing electronic, conformational, steric, and stereoelectronic effects. Relying on these factors, highly regio- and chemoselective carbene insertion reaction of C-H bonds in different environments could be obtained. The observed selectivity clearly indicates that an electronic effect plays a more important role than steric effect. In general, C-H bonds in conformationally rigid cyclic environments are less reactive than those in acyclic systems toward carbene insertion, and in this situation, a competing intermolecular reaction between alkylidene carbene and trimethylsilyldiazomethane led to the formation of allenylsilanes. The formation of allenylsilane becomes more favorable as the concentration of reaction becomes higher, as well as the C-H bonds undergoing insertion becomes electronically and conformationally deactivated.