(+/-)-4,4-Dimethyl-6-hepten-1-yn-3-ol | 115246-70-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-4,4-Dimethyl-6-hepten-1-yn-3-ol
• 英文别名: 4,4-Dimethylhept-6-en-1-yn-3-ol
• CAS: 115246-70-3
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: NUZYLGNPFMPNOZ-UHFFFAOYSA-N

物化性质

• 沸点：
  199.8±28.0 °C(Predicted)
• 密度：
  0.898±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  (+/-)-4,4-Dimethyl-6-hepten-1-yn-3-ol 在 正丁基锂 、 potassium hydride 作用下， 反应 6.08h， 生成 5,5-dimethyl-1-methoxy-4-((p-methoxybenzyl)oxy)-7-octen-3-yne
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1

  摘要：

  Enhancing synthetic efficiency requires the development of synthetic reactions that, to the extent possible, are simple additions wherein everything else is required only in catalytic amounts. The Alder ene reaction constitutes a classical reaction that meets this requirement that has much unrealized potential. A transition-metal-catalyzed version helps to increase that potential by permitting this reaction to proceed under mild conditions. A significant benefit of transition metal catalysis is the feasibility of diverting the reaction along pathways not feasible under thermal conditions. The synthesis of 1,3-dienes rather than 1,4-dienes is a very important diversion because of the utility of 1,3-dienes as reaction partners in the Diels-Alder reaction, another highly atom economical process. A catalyst derived from palladium acetate cycloisomerizes 1,6- and 1,7-enynes to dialkylidenecyclopentanes and -cyclohexanes. 1,3-Diene formation is favored over the Alder ene process by both steric and electronic effects. The reaction is highly chemoselective-tolerating a wide diversity of functionality including hydroxyl groups, ketones, esters, alkynyl and enol ethers, alkynyl and vinyl silanes, and enones. Many of the substrates are available by palladium-catalyzed alkylation reactions-highlighting the effectiveness of palladium catalyzed methodology in organic synthesis. The atom-economical nature of these reactions combined with the Diels-Alder reaction permit butadiene and dimethyl propargylmalonate to be molded into a polyhydro-as-indacene. The mechanism of this reaction may involve a tautomerization of an enyne-Pd(+2) complex to a pallada(+4)cyclopentene intermediate as a key step.

  DOI：

  10.1021/ja00089a015
• 作为产物：
  描述：

  2,2-二甲基-4-戊烯醛 在 氢氧化钾 、 正丁基锂 作用下， 反应 3.0h， 生成 (+/-)-4,4-Dimethyl-6-hepten-1-yn-3-ol
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1

  摘要：

  Enhancing synthetic efficiency requires the development of synthetic reactions that, to the extent possible, are simple additions wherein everything else is required only in catalytic amounts. The Alder ene reaction constitutes a classical reaction that meets this requirement that has much unrealized potential. A transition-metal-catalyzed version helps to increase that potential by permitting this reaction to proceed under mild conditions. A significant benefit of transition metal catalysis is the feasibility of diverting the reaction along pathways not feasible under thermal conditions. The synthesis of 1,3-dienes rather than 1,4-dienes is a very important diversion because of the utility of 1,3-dienes as reaction partners in the Diels-Alder reaction, another highly atom economical process. A catalyst derived from palladium acetate cycloisomerizes 1,6- and 1,7-enynes to dialkylidenecyclopentanes and -cyclohexanes. 1,3-Diene formation is favored over the Alder ene process by both steric and electronic effects. The reaction is highly chemoselective-tolerating a wide diversity of functionality including hydroxyl groups, ketones, esters, alkynyl and enol ethers, alkynyl and vinyl silanes, and enones. Many of the substrates are available by palladium-catalyzed alkylation reactions-highlighting the effectiveness of palladium catalyzed methodology in organic synthesis. The atom-economical nature of these reactions combined with the Diels-Alder reaction permit butadiene and dimethyl propargylmalonate to be molded into a polyhydro-as-indacene. The mechanism of this reaction may involve a tautomerization of an enyne-Pd(+2) complex to a pallada(+4)cyclopentene intermediate as a key step.

  DOI：

  10.1021/ja00089a015

文献信息

• Tandem Cyclization of Alkynes via Rhodium Alkynyl and Alkenylidene Catalysis
  作者：Jung Min Joo、Yu Yuan、Chulbom Lee

  DOI：10.1021/ja066374v

  日期：2006.11.1

  A rhodium(I)-catalyzed tandem cyclization of alkynes has been developed. The reaction allows for multiple bond formations to occur at both the alpha- and beta-positions of alkynes under mild conditions to yield a variety of fused ring systems as the products. In the presence of triethylamine and the complex derived from [Rh(COD)Cl]2 and P(4-F-C6H4)3, a terminal alkyne is converted to a rhodium alkynyl

  已经开发了铑（I）催化的炔烃串联环化。该反应允许在温和条件下在炔烃的 α 位和 β 位形成多个键，以产生各种稠环系统作为产物。在三乙胺和衍生自 [Rh(COD)Cl]2 和 P(4-F-C6H4)3 的络合物的存在下，末端炔转化为铑炔基物质，该物质与束缚的烷基卤在 β-位置以提供 β,β-二取代亚烯基复合物。然后，铑亚烯基物质分别通过 [2 + 2] 环加成、亲核加成和 6pi 电环化过程与一系列侧链官能团（如烯烃、羟基和苯基）发生额外的闭环。
• A short enantioselective synthesis of (+)-sterpurene: complete intramolecular transfer of central to axial to central chiral elements
  作者：Richard A. Gibbs、William H. Okamura

  DOI：10.1021/ja00220a069

  日期：1988.6

  L'etape cle de la synthese est une addition de Diels Alder intramoleculaire et stereoselective du (dimethyl-4,4 methyl-2' cyclobutene-1'yl-1) heptene-6yne-1ol-3, obtenu a partir du dimethyl-4,4 heptene-6yne-1ol-3

  L'etape cle de la synthese est une added de Diels Alder intramoleculaire et立体选择性 du (dimethyl-4,4methyl-2' cyclobutene-1'yl-1) heptene-6yne-1ol-3, obtenu a partir du dimethyl-4 ,4 庚烯-6yne-1ol-3
• Reactivity Pattern of Bis(propargyloxy) Disulfides: Tandem Rearrangements and Cyclizations
  作者：Samuel Braverman、Tatiana Pechenick-Azizi、Hugo Gottlieb、Milon Sprecher

  DOI：10.1055/s-0030-1260024

  日期：2011.6

  pattern of the reactant. Inter alia they undergo surprising tandem sigmatropic rearrangements and cycloadditions. Three heretofore unknown product types were isolated and fully characterized: 6,7-dithiabicyclo[3.1.1]heptan-2-one 6-oxide derivatives, two isomeric 1,2-dithiete 1,1-dioxides (α,β-unsaturated four-membered cyclic thiosulfonates) from bis(propargyloxy) disulfides with α- or γ-alkyl-substituted

  成功制备了35个取代的双（炔丙基氧基）二硫化物，收率好至极好，发现它们的反应性强烈依赖于反应物的取代方式。它们尤其经历令人惊讶的串联σ重排和环加成。分离出三种迄今未知的产物类型，并对其进行了全面表征：6,7-二硫代双环[3.1.1]庚烷-2-一6-氧化物衍生物，两种同分异构的1,2-二硫代1,1-二氧化物（α，β-不饱和四双（炔丙基氧基）二硫化物带有α-或γ-烷基取代的炔丙基的二元环硫代磺酸盐，和双（炔丙基氧基）二硫化物的两个异构体2-氧杂5,7-二硫杂双环[2.2.1]庚烷5-氧化物具有α-叔丁基-或α，α-二烷基取代的炔丙基。 σ重排-环加成-取代基的效果-双（炔丙氧基）二硫化物- dithiabicyclic结构-有机硫化学-硫代磺酸酯- VIC -disulfoxides
• An enantioselective central-axial-central chiral element transfer process leading to a concise synthesis of (+)-sterpurene: intramolecular Diels-Alder reactions of vinylallene sulfoxides
  作者：Richard A. Gibbs、Karin Bartels、Robert W. K. Lee、William H. Okamura

  DOI：10.1021/ja00192a033

  日期：1989.5

  The intramolecular Diels-Alder (IMDA) reaction of vinylallene sulfoxide 19 as the diene component occurs in a rapid and stereoselective manner at room temperature to give tricyclic 20 in good yield. Sulfoxide 19 cyclizes approximately} 140 times faster than the corresponding hydrocarbon 15a. It was also shown that gem-dimethyl substitution on the tether linking the vinylallene and vinyl group accelerates

  作为二烯组分的乙烯基丙二烯亚砜 19 的分子内狄尔斯-阿尔德 (IMDA) 反应在室温下以快速和立体选择性的方式发生，以良好的产率得到三环 20。亚砜 19 环化大约}比相应的碳氢化合物 15a 快 140 倍。还表明，连接乙烯基丙二烯和乙烯基的系链上的偕二甲基取代仅使环化速率加快了 大约} 2.6 倍。用苯亚磺酰氯处理富含对映异构体的二烯炔丙醇 6 得到乙烯亚砜 4，其以高度对映选择性和非对映选择性方式环化，得到旋光三环亚砜 5。亚砜 5 分两步转化为新型倍半萜真菌代谢物 (+)- sterpurene，从而建立其绝对构型。
• Reactions of Ruthenium Cp Phosphine Complex with 4,4-Disubstituted-1,6-Enynes: Effect of Methyl Substituents in the Olefinic Fraction
  作者：Chia-Pei Chung、Chien-Chih Chen、Ying-Chih Lin、Yi-Hong Liu、Yu Wang

  DOI：10.1021/ja906745j

  日期：2009.12.30

  associated with propargylic alcohol and the olefinic group has various substituted methyl groups. For the enyne compounds 1-3 with no substituted methyl group, the reaction takes place at the propargylic alcohol first giving the allenylidene complex 6 which could undergo a skeletal rearrangement to yield the disubstituted vinylidene complex 7. By changing the propargylic alcohol to propargylic ether, the

  我们研究了 Cp(PPh(3))(2)RuCl 与九种 1,6-烯炔化合物（1-4、8、12、19、21 和 22）的化学反应，其中三键与炔丙醇相关并且烯基具有各种取代的甲基。对于没有取代甲基的烯炔化合物 1-3，首先在炔丙醇处发生反应，得到丙炔配合物 6，该配合物可以进行骨架重排，得到二取代的亚乙烯基配合物 7。通过将炔丙醇变成炔丙醚，该反应通过环化反应得到作为主要产物的卡宾配合物10和作为次要产物的丁二烯配合物9。对于在烯烃部分的末端碳上具有两个甲基的烯炔 12，通过使用溶剂来控制在Cα处具有取代环戊烯基环的卡宾配合物15和16或亚乙烯基配合物17的形成。对于 15 和 16 的形成，建议在 Cbeta 的中间体中发生 CC 键形成环化反应，其中三键是 pi 配位的。然而，对于亚乙烯基中间体，反应可以通过形成亚丙叉基进行，亚丙叉基进行逆烯反应，导致二甲基取代的烯丙基裂解，得到 17。对于两个烯炔