2-phenyl-5-methyl-7-oxabicyclo<3.3.0>oct-1-en-3-one

• 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-phenyl-5-methyl-7-oxabicyclo<3.3.0>oct-1-en-3-one
• 英文别名: 5-methyl-2-phenyl-7-oxabicyclo[3.3.0]oct-1-en-3-one；3a,4-dihydro-3a-methyl-6-phenyl-1H-cyclopenta[c]furan-5(3H)-one；3a-methyl-6-phenyl-3,4-dihydro-1H-cyclopenta[c]furan-5-one
• 化学式: C₁₄H₁₄O₂
• 分子量: 214.264
• InChiKey: ZXXCEOAEQAWSPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (3-((2-methylallyl)oxy)prop-1-yn-1-yl)benzene 在 bis(cyclopentadienyl)bis(trimethylphosphane)titanium(II) 、 copper(II) sulfate 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 52.0h， 生成 2-phenyl-5-methyl-7-oxabicyclo<3.3.0>oct-1-en-3-one
  参考文献：
  名称：

  Development of a Titanocene-Catalyzed Enyne Cyclization/Isocyanide Insertion Reaction

  摘要：

  The first early transition metal-catalyzed enyne cyclization reaction is described. The system converts enyne substrates to bicyclic iminocyclopentenes through the use of 10 mol % of Cp(2)Ti(PMe(3))(2) in the presence of a silyl cyanide. Subsequent hydrolysis produces the corresponding bicyclic cyclopentenones in good overall yield. The cyclization reaction is tolerant of polar functional groups such as ethers, amines, and esters and is diastereoselective with certain chiral enyne substrates.

  DOI：

  10.1021/ja00098a020

文献信息

• CO-Transfer Carbonylation Reactions. A Catalytic Pauson−Khand-Type Reaction of Enynes with Aldehydes as a Source of Carbon Monoxide
  作者：Tsumoru Morimoto、Koji Fuji、Ken Tsutsumi、Kiyomi Kakiuchi

  DOI：10.1021/ja0126881

  日期：2002.4.1

  The reaction of enynes with aldehydes in the presence of a catalytic amount of [RhCl(cod)](2)/dppp results in the Pauson-Khand-type reaction without the use of gaseous carbon monoxide to give bicyclic cyclopentenones in high yields (14 examples). Aldehydes serve as a source of carbon monoxide, and their carbonyl moiety is transferred to enynes, resulting in the formation of the carbonylated products

  在催化量的 [RhCl(cod)](2)/dppp 存在下，烯炔与醛的反应会导致 Pauson-Khand 型反应，而无需使用气态一氧化碳，以高产率得到双环环戊烯酮 (14例子）。醛作为一氧化碳的来源，它们的羰基部分被转移到烯炔，导致形成羰基化产物。该反应代表了 CO 转移羰基化的第一个例子。
• Rhodium-Catalyzed Pauson-Khand-Type Reaction Using Alcohol as a Source of Carbon Monoxide
  作者：Ji Hoon Park、Yoonhee Cho、Young Keun Chung

  DOI：10.1002/anie.201001246

  日期：2010.7.12

  cyclopentenones have been synthesized from enynes in alcohol in the presence of a rhodium catalyst through a newly developed auto‐tandem catalytic reaction. This process combines three mechanistically distinctive reactions—an oxidation of alcohols, a decarbonylation of aldehydes, and a carbonylative [2+2+1] cycloaddition (see scheme; dppp=propane‐l,3‐diylbis(diphenylphosphane)).

  三合一锅！双环环戊烯酮是在铑催化剂存在下，通过新开发的自动串联催化反应，由炔烃在醇中合成的。此过程结合了三个机械上独特的反应-醇的氧化，醛的脱羰基和羰基化的[2 + 2 + 1]环加成反应（请参见方案； dppp =丙烷-1,3-二联双（二苯基膦））。
• Intramolecular Pauson–Khand reaction catalyzed by oxime-derived palladacycles
  作者：Xue-Rui Wang、Fu-Hua Lu、Yang Song、Zhong-Lin Lu

  DOI：10.1016/j.tetlet.2011.11.106

  日期：2012.2

  Oxime-derived palladacycles were successfully applied as a novel class of catalysts in the intramolecular Pauson–Khand reactions. Allylpropargyl ethers and allylpropargyl amines can be efficiently converted to the cyclopentenone products with good to excellent yields.

  肟衍生的palladacycles被成功地用作分子内Pauson-Khand反应中的一类新型催化剂。烯丙基炔丙基醚和烯丙基炔丙基胺可以有效地转化为环戊烯酮产物，收率良好或优异。
• Utilization of Aldoses as a Carbonyl Source in Cyclocarbonylation of Enynes
  作者：Keiichi Ikeda、Tsumoru Morimoto、Kiyomi Kakiuchi

  DOI：10.1021/jo1012288

  日期：2010.9.17

  The reaction of enynes with acetyl-masked aldoses in the presence of a rhodium(I) catalyst resulted in cyclocarbonylation, thus avoiding the direct use of carbon monoxide, to afford bicyclic cyclopentenones. In rhodium catalysis, aldoses serve as a carbon monoxide equivalent by donating their carbonyl moieties on the acyclic aldehyde form to enynes. A variety of aldoses, including d-glucose, d-mannose

  在铑（I）催化剂存在下，烯炔与乙酰基掩盖的醛糖的反应导致环羰基化，从而避免了直接使用一氧化碳，得到双环环戊烯酮。在铑催化中，醛糖通过将其在无环醛形式上的羰基部分提供给烯炔而充当一氧化碳当量。可以使用多种醛糖，包括d-葡萄糖，d-甘露糖，d-半乳糖，d-木糖和d-核糖，作为羰基来源。使用该方法，各种烯类都以22-67％的收率被环羰基化。不对称变体也以中等至高对映选择性进行。
• Rh(I)-Catalyzed Cyclocarbonylation of Enynes with Glyceraldehyde: An Available Carbonyl Source Derived from Sugar Alcohols
  作者：Tsumoru Morimoto、Keiichi Ikeda、Takayuki Tsumagari、Hiroki Tanimoto、Yasuhiro Nishiyama、Kiyomi Kakiuchi

  DOI：10.1055/s-0031-1290311

  日期：2012.2

  Catalytic cyclocarbonylation reactions using a glyceraldehyde derivative as a carbonyl source are described. The rhodium(I)-catalyzed reaction of enynes with glyceraldehyde acetonide gave bicyclic cyclopentenones as the products. This presents an interesting use of a sugar alcohol derived carbon resource as well as a convenient procedure for the cyclocarbonylation of enynes. rhodium - cyclocarbonylation

  描述了使用甘油醛衍生物作为羰基源的催化环羰基化反应。炔烃与甘油醛丙酮化物的铑（I）催化反应得到双环环戊烯酮。这提供了糖醇衍生的碳资源的有趣用途以及烯炔的环羰基化的简便方法。 铑-环羰基化-烯炔-甘油醛-糖醇