2-(1-Hydroxy-5-hexenyl)-1-<2-(trimethylsilyl)ethynyl>benzene | 166757-18-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(1-Hydroxy-5-hexenyl)-1-<2-(trimethylsilyl)ethynyl>benzene
• 英文别名: 1-[2-(2-Trimethylsilylethynyl)phenyl]hex-5-en-1-ol
• CAS: 166757-18-2
• 化学式: C₁₇H₂₄OSi
• 分子量: 272.462
• InChiKey: UFBQSQQNZDRSPW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.31
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(1-Hydroxy-5-hexenyl)-1-<2-(trimethylsilyl)ethynyl>benzene 在 copper(l) iodide 、 bis(triphenylphosphine)palladium(II)-chloride 、 四丁基氟化铵 、 三乙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 42.0h， 生成 Methyl 2-<2-<2-(1-oxo-5-hexenyl)phenyl>ethynyl>benzoate
  参考文献：
  名称：

  An Unusual Example of a 6-Endo-Dig Addition to an Unactivated Carbon-Carbon Triple Bond

  摘要：

  Methyl 2-[2-[2-(1-hydroxy-1-ethyl)phenyl]ethynyl]benzoate was prepared as an intermediate for subsequent conversion to an a-diazo ketone. Under the basic conditions used to hydrolyze the methyl ester, the neighboring hydroxyl functionality underwent reaction with the unactivated acetylenic group, producing a benzopyranyl-substituted alpha-diazoacetophenone. Treatment of this diazocarbonyl compound with a catalytic quantity of rhodium(II) mandelate afforded a novel dibenzo[a,e]cyclononenone derivative. The reaction proceeds via an initially formed oxonium ylide which rearranges further by means of a 1,2-alkyl shift. A prime factor in determining the direction of internal cyclization to the triple bond is the presence of the carbomethoxy group in the ortho position of the beta-phenyl ring. Thus, in contrast with related systems which exhibit a clear preference for 5-exo-dig cyclization at the acetylenic center, the 6-endo-dig addition is the preferred pathway for the o-formyl- and o-carbomethoxy-substituted alkynyl alcohols. Careful monitoring of the reaction actually showed that the reaction proceeds by initial formation of the 5-exo-dig product followed by a novel rearrangement to the 6-endo product.

  DOI：

  10.1021/jo00122a047
• 作为产物：
  描述：

  邻溴苯甲醛 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 碘 、 magnesium 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 2-(1-Hydroxy-5-hexenyl)-1-<2-(trimethylsilyl)ethynyl>benzene
  参考文献：
  名称：

  通过串联二吡啶（II）催化的三唑脱氮和[3 + 2]环加成反应立体合成氧杂双环[2.2.1]庚烯

  摘要：

  已经开发出了一种新的合成策略，用于非对映选择性合成结构多样的氧杂双环[2.2.1]庚烯，其特征是串联反应结合了Rh催化的三唑脱氮和新型的[3 + 2]环加成反应。该串联反应被认为是通过五元氧鎓叶立德中间体进行的，该中间体由α-亚氨基茂金属上羰基的分子内亲核进攻，然后是分子间或分子内[3 + 2]双极性环加成而形成。炔烃和烯烃的范围。

  DOI：

  10.1021/acs.orglett.6b02703

文献信息

• Stereoselective Synthesis of Oxabicyclo[2.2.1]heptenes via a Tandem Dirhodium(II)-Catalyzed Triazole Denitrogenation and [3 + 2] Cycloaddition
  作者：Hao Yuan、Jianxian Gong、Zhen Yang

  DOI：10.1021/acs.orglett.6b02703

  日期：2016.11.4

  A novel synthetic strategy for the diastereoselective synthesis of structurally diverse oxabicyclo[2.2.1]heptenes has been developed, featuring a tandem reaction combining a Rh-catalyzed triazole denitrogenation and a novel type of [3 + 2] cycloaddition reaction. This tandem reaction was thought to proceed via a five-membered oxonium ylide intermediate, which was formed by the intramolecular nucleophilic

  已经开发出了一种新的合成策略，用于非对映选择性合成结构多样的氧杂双环[2.2.1]庚烯，其特征是串联反应结合了Rh催化的三唑脱氮和新型的[3 + 2]环加成反应。该串联反应被认为是通过五元氧鎓叶立德中间体进行的，该中间体由α-亚氨基茂金属上羰基的分子内亲核进攻，然后是分子间或分子内[3 + 2]双极性环加成而形成。炔烃和烯烃的范围。
• An Efficient Gold-Catalyzed Domino Process for the Construction of Tetracyclic Ketoethers
  作者：Tobias Groß、Peter Metz

  DOI：10.1002/chem.201302985

  日期：2013.10.25

  Au, yeah! Catalytic amounts of gold(III)chloride allow a mild and efficient oxidative domino cyclization/cycloaddition of enyne carbonyl compounds 1 and 4 to give the tetracycles 2 or 5, respectively, in the presence of pyridine N‐oxide 3 (see scheme; DCE = 1,2‐dichloroethane).

  哦，是的！在吡啶N-氧化物3存在下，催化量的氯化金（III）可以温和有效地氧化烯炔羰基化合物1和4进行氧化多米诺环化/环加成，分别生成四环2或5（参见方案; DCE = 1,2-二氯乙烷）。
• Discovery of a Photoinduced Dark Catalytic Cycle Using <i>in Situ</i> LED-NMR Spectroscopy
  作者：Dan Lehnherr、Yining Ji、Andrew J. Neel、Ryan D. Cohen、Andrew P. J. Brunskill、Junyu Yang、Mikhail Reibarkh

  DOI：10.1021/jacs.8b08596

  日期：2018.10.24

  We report the use of LED-NMR spectroscopy to study the reaction mechanism of a newly discovered photoinduced iron-catalyzed cycloisomerization of alkynols to cyclic enol ethers. By understanding on/off ligand binding to the catalyst, we were able to appropriately design reaction conditions to balance catalyst activity and stability. LED-NMR was demonstrated to be a powerful tool in elucidating reaction mechanisms of photochemical reactions. Temporal NMR spectroscopic data under visible light illumination (1) revealed the pre-catalyst activation mechanism, (2) proved that photon flux provides a unique external control of the equilibrium distribution between the pre-catalyst and active catalyst, and ultimately the rate of reaction, (3) provided information about the reaction driving forces and the turnover-limiting step, and (4) enabled both real-time structural and kinetic insights into elusive species (e.g., dissolved gases).
• An Unusual Example of a 6-Endo-Dig Addition to an Unactivated Carbon-Carbon Triple Bond
  作者：Albert Padwa、Keith E. Krumpe、M. David Weingarten

  DOI：10.1021/jo00122a047

  日期：1995.9

  Methyl 2-[2-[2-(1-hydroxy-1-ethyl)phenyl]ethynyl]benzoate was prepared as an intermediate for subsequent conversion to an a-diazo ketone. Under the basic conditions used to hydrolyze the methyl ester, the neighboring hydroxyl functionality underwent reaction with the unactivated acetylenic group, producing a benzopyranyl-substituted alpha-diazoacetophenone. Treatment of this diazocarbonyl compound with a catalytic quantity of rhodium(II) mandelate afforded a novel dibenzo[a,e]cyclononenone derivative. The reaction proceeds via an initially formed oxonium ylide which rearranges further by means of a 1,2-alkyl shift. A prime factor in determining the direction of internal cyclization to the triple bond is the presence of the carbomethoxy group in the ortho position of the beta-phenyl ring. Thus, in contrast with related systems which exhibit a clear preference for 5-exo-dig cyclization at the acetylenic center, the 6-endo-dig addition is the preferred pathway for the o-formyl- and o-carbomethoxy-substituted alkynyl alcohols. Careful monitoring of the reaction actually showed that the reaction proceeds by initial formation of the 5-exo-dig product followed by a novel rearrangement to the 6-endo product.
• Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐ <i>o</i> ‐quinodimethanes ( <scp> Vinyl‐ <i>o</i> ‐QDMs </scp> ) ^†
  作者：Hejiang Luo、Chuan He、Huanfeng Jiang、Shifa Zhu

  DOI：10.1002/cjoc.202000144

  日期：2020.10

  A Cu(I)‐catalyzed three‐component reaction of terminal enynals/enynones, diazo compounds, and alkenes has been developed. With this method, a series of oxabicyclo[2.2.2]octanes were effectively synthesized in high yields under mild reaction conditions. This transformation is proposed to proceed through trapping of the cyclic vinyl‐o‐quinodimethanes (vinyl‐o‐QDMs) species, which were generated from

  已经开发了一种铜（I）催化的末端烯醇/烯酮，重氮化合物和烯烃的三组分反应。用这种方法，在温和的反应条件下，可以高产率有效地合成一系列氧杂双环[2.2.2]辛烷。该变换是通过提出环状乙烯基的俘获进行ö -quinodimethanes（乙烯基ö -QDMs）种，其中，从终端enynals / enynones和由烯烃重氮化合物生成。广泛的底物范围，温和的反应条件，高的对映选择性和原子效率等明显优点使该反应对于构建高刚性[2.2.2]辛烷骨架具有很高的吸引力。