2,6-dimethyl-5-methylene-hepta-1,6-dien-3-yne | 263394-35-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 2,6-dimethyl-5-methylene-hepta-1,6-dien-3-yne
• 英文别名: 2,6-Dimethyl-5-methylidenehepta-1,6-dien-3-yne
• CAS: 263394-35-0
• 化学式: C₁₀H₁₂
• 分子量: 132.205
• InChiKey: KKUJPZUVPOUPNW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.2
• 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：

  2,6-dimethyl-5-methylene-hepta-1,6-dien-3-yne 以 苯 为溶剂， 反应 5.0h， 生成 (R)-2,4-Dimethyl-1,4-bis-(3-methyl-but-3-en-1-ynyl)-cyclohexene
  参考文献：
  名称：

  Chemo- and Regioselective Dimerization of Terminal Alkynes Promoted by Methylaluminoxane

  摘要：

  Methylalumoxane (MAO) was found to be an active catalytic precursor for the chemo- and regioselective dimerization of a wide range of aryl- and alkyl-substituted terminal alkynes yielding the corresponding geminal dimers A. For an olefin-functionalized terminal alkyne (RC=CH, R = MeC=CH2), the geminal dimer undergoes an intermolecular [4 + 2] cycloaddition forming compound B.

  DOI：

  10.1021/ol9903584
• 作为产物：
  描述：

  2-甲基-1-丁烯-3-炔 在 吡啶 、 RhCl(1,3-bis-(2,6-diisopropylphenyl)imidazol-2-carbene)(η²-cyclooctene)(pyridine) 作用下， 以 甲苯 为溶剂， 生成 2,6-dimethyl-5-methylene-hepta-1,6-dien-3-yne
  参考文献：
  名称：

  铑-吡啶-N-杂环碳烯催化剂促进的炔烃与甲硅烷基乙炔的宝石选择性交叉二聚和交叉三聚

  摘要：

  所述偕选择性交叉二聚化和与炔silylacetylenes的-trimerization至C 使用铑ħ激活（I）-pyridine- ñ -杂环卡宾催化剂已被开发。该反应应用于各种脂肪族或芳香族末端炔烃，内炔，和宝石-1,3-二取代烯炔，得到相应的烯炔和dienynes具有高区域选择性和立体选择性和良好的分离产率（高达91％）。

  DOI：

  10.1002/cctc.201402327

文献信息

• Pyridine-Enhanced Head-to-Tail Dimerization of Terminal Alkynes by a Rhodium-N-Heterocyclic-Carbene Catalyst
  作者：Laura Rubio-Pérez、Ramón Azpíroz、Andrea Di Giuseppe、Victor Polo、Ricardo Castarlenas、Jesús J. Pérez-Torrente、Luis A. Oro

  DOI：10.1002/chem.201302079

  日期：2013.11.4

  rhodium‐catalyzed head‐to‐tail dimerization of terminal alkynes is presented. The presence of a pyridine ligand (py) in a Rh–N‐heterocyclic‐carbene (NHC) catalytic system not only dramatically switches the chemoselectivity from alkyne cyclotrimerization to dimerization but also enhances the catalytic activity. Several intermediates have been detected in the catalytic process, including the π‐alkyne‐coordinated RhI

  本文介绍了一般的区域选择性铑催化的炔烃头到尾二聚化反应。Rh-N-杂环卡宾（NHC）催化系统中吡啶配体（py）的存在不仅将化学选择性从炔烃环三聚转变为二聚，而且还增强了催化活性。几个中间体已在催化过程中检测到，包括π-炔配位的铑我物种[的RhCl（NHC）（η 2 -HCCCH 2 PH）（PY）]（3）和[的RhCl（NHC）η 2 -C（吨丁基）C（é）CHCH吨卜}（PY）]（4）和RH III -hydride炔基物种[RhClH  CCSi（ME）3 }（IPR）（PY）2 ]（5）。计算DFT研究揭示由顺序炔C的运行机制 ħ氧化加成，炔插入和还原消除。根据头对尾选择性，炔烃的2,1-加氢金属化是更有利的途径。
• Chemo- and Regioselective Dimerization of Terminal Alkynes Promoted by Methylaluminoxane
  作者：Aswini K. Dash、Moris S. Eisen

  DOI：10.1021/ol9903584

  日期：2000.3.1

  Methylalumoxane (MAO) was found to be an active catalytic precursor for the chemo- and regioselective dimerization of a wide range of aryl- and alkyl-substituted terminal alkynes yielding the corresponding geminal dimers A. For an olefin-functionalized terminal alkyne (RC=CH, R = MeC=CH2), the geminal dimer undergoes an intermolecular [4 + 2] cycloaddition forming compound B.
• <i>gem</i>-Selective Cross-Dimerization and Cross-Trimerization of Alkynes with Silylacetylenes Promoted by a Rhodium-Pyridine-<i>N</i>-Heterocyclic Carbene Catalyst
  作者：Ramón Azpíroz、Laura Rubio-Pérez、Ricardo Castarlenas、Jesús J. Pérez-Torrente、Luis A. Oro

  DOI：10.1002/cctc.201402327

  日期：2014.9

  The gem‐selective cross‐dimerization and ‐trimerization of silylacetylenes with alkynes through CH activation using a rhodium(I)–pyridine–N‐heterocyclic carbene catalyst have been developed. This reaction is applied to various aliphatic or aromatic terminal alkynes, internal alkynes, and gem‐1,3‐disubsituted enynes to afford the corresponding enynes and dienynes with high regio‐ and stereoselectivities

  所述偕选择性交叉二聚化和与炔silylacetylenes的-trimerization至C 使用铑ħ激活（I）-pyridine- ñ -杂环卡宾催化剂已被开发。该反应应用于各种脂肪族或芳香族末端炔烃，内炔，和宝石-1,3-二取代烯炔，得到相应的烯炔和dienynes具有高区域选择性和立体选择性和良好的分离产率（高达91％）。