3-(2-propenyl)cycloheptanone | 77802-58-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(2-propenyl)cycloheptanone
• 英文别名: 3-allylcycloheptanone；3-prop-2-enylcycloheptan-1-one
• CAS: 77802-58-5
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: PUJNRAQFBBUJEC-UHFFFAOYSA-N

物化性质

• 沸点：
  225.1±9.0 °C(Predicted)
• 密度：
  0.896±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-(2-propenyl)cycloheptanone 在 titanium(IV) isopropylate 、 盐酸羟胺 、 sodium acetate 、 sodium hydride 、 对甲苯磺酰氯 作用下， 以 四氢呋喃 、 乙醇 、 乙腈 为溶剂， 反应 0.58h， 生成 2-(4-methoxybenzyl)-2-azatricyclo[5.3.1.0^1,9]undecane
  参考文献：
  名称：

  Bredt规则捕获的Kulinkovich-de Meijere反应的碳环氨基酮

  摘要：

  Ti II介导的由烯烃和酰胺形成的环丙胺，Kulinkovich-de Meijere反应涉及两个碳-碳键形成步骤。如果第二步需要形成桥头双键，则三环中间体的战略性使用可中止该过程。使用此Bredt规则约束会产生碳环氨基酮（关键生物碱构件）的产生。

  DOI：

  10.1002/anie.201509983
• 作为产物：
  描述：

  2-环庚烯-1-酮 、 烯丙基三甲基硅烷 在 indium 、 三甲基氯硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以72%的产率得到3-(2-propenyl)cycloheptanone
  参考文献：
  名称：

  使用催化铟和三甲基氯硅烷将烯丙基硅烷高效添加到 α,β-烯酮中

  摘要：

  α,β-烯酮与烯丙基三甲基硅烷发生有效的 Hosomi-Sakurai 反应，其中催化量的铟在三甲基氯硅烷作为活化剂的存在下在温和条件下以良好的产率产生共轭加成产物。

  DOI：

  10.1055/s-2003-41017

文献信息

• Studies on the reactions of α,β-enones with allyl indium reagent; effects of TMSCl as promoter on regioselectivity
  作者：Phil Ho Lee、Hyosoon Ahn、Kooyeon Lee、Sun-young Sung、Sunggak Kim

  DOI：10.1016/s0040-4039(00)01872-4

  日期：2001.1

  Regioselectivity on the reactions of α,β-enones with allyl indium reagents in the presence of TMSCl was systematically studied. 2-Cyclohexen-1-one, (R)-carvone, 2-cyclohepten-1-one and chalcone produced 1,4-addition products in good yields, whereas 2-cyclopenten-1-one, 2-methylcyclopenten-1-one, 4,4-dimethylcyclohexen-1-one and acyclic α,β-enones afforded 1,2-addition products.

  系统地研究了在TMSC1存在下，α，β-烯键与烯丙基铟试剂反应的区域选择性。2-环己烯-1-酮，（R）-香芹酮，2-环庚烯-1-酮和查尔酮可产生高产率的1,4-加成产物，而2-环戊烯-1-酮，2-甲基环戊烯-1-酮，4，4-二甲基环己烯-1-酮和无环α，β-烯酮提供1，2-加成产物。
• Intramolecular cycloaddition reactions of exocyclic nitrones
  作者：Raymond L. Funk、Gary L. Bolton、Joy Umstead Daggett、Marvin M. Hansen、Linus H.M. Horcher

  DOI：10.1016/s0040-4020(01)96702-x

  日期：1985.1

  Exocyclic nitrones smoothly participate in intramolecular cycloaddition reactions to provide bridged and fused polycarbocycles. The exploitation of this methodology in the total syntheses of the sesquiterpenes (±)-7,12-secoishwaran-12-ol (44), (±)-hirsutene (56), (±)-coriolin (68) is also presented.

  环外硝酮平稳地参与分子内环加成反应，以提供桥连和稠合的多碳环。还介绍了该方法在倍半萜（±）-7,12-secoishwaran-12-ol（44），（±）-hirsutene（56），（±）-coriolin（68）的总合成中的应用。
• Allylbarium Reagents: Unprecedented Regio- and Stereoselective Allylation Reactions of Carbonyl Compounds
  作者：Akira Yanagisawa、Shigeki Habaue、Katsutaka Yasue、Hisashi Yamamoto

  DOI：10.1021/ja00093a010

  日期：1994.7

  The first direct preparation of allylbarium reagents by reaction of insitu generated reactive barium with various allylic chlorides and their new and unexpected selective allylation reactions with carbonyl compounds are disclosed. Highly reactive barium was readily prepared by the reduction of barium iodide with 2 equiv of lithium biphenylide in dry THF at room temperature. A variety of carbonyl compounds reacted with barium reagents generated from (E)- or (Z)-allylic chlorides in THF at -78 degrees C. All reactions resulted in high yields with remarkable alpha-selectivities not only with aldehydes but also with ketones. The double bond geometry of the starting allylic chloride was completely retained in each case. Stereochemically homogeneous (E)- and (Z)beta,gamma-unsaturated carboxylic acids were easily prepared in good yields by highly alpha-selective carboxylation of allylic barium reagents with carbon dioxide. A selective Michael addition reaction with alpha,beta-unsaturated cycloalkanone was also achieved using an allylbarium reagent. Treatment of 2-cyclopentenone (1 equiv) with allylbarium chloride (2 equiv) in THF at -78 degrees C for 20 min afforded 3-allylcyclopentanone in 94% yield with a 1,4/1,2 ratio of >99/1. Furthermore, the in situ generated barium enolate was efficiently trapped with various kinds of electrophiles (Me(2)C=CHCH2Br, (C5H11CHO)-C-n, and CH3COCl).
• A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction
  作者：Gary A. Molander、Jeffrey A. McKie

  DOI：10.1021/jo00013a008

  日期：1991.6

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.
• Facile bridged bicycloalkane synthesis via intramolecular nitrone-olefin cycloaddition
  作者：Raymond L. Funk、Linus H. M. Horcher、Joy Umstead Daggett、Marvin M. Hansen

  DOI：10.1021/jo00163a052

  日期：1983.7