5,5-dimethylcyclopent-2-enone | 17197-84-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,5-dimethylcyclopent-2-enone
• 英文别名: 5,5-dimethyl-2-cyclopentenone；2-Cyclopenten-1-one, 5,5-dimethyl-；5,5-dimethylcyclopent-2-en-1-one
• CAS: 17197-84-1
• 化学式: C₇H₁₀O
• 分子量: 110.156
• InChiKey: OUDVKHIZRZRHGO-UHFFFAOYSA-N

物化性质

• 沸点：
  155-160 °C
• 密度：
  0.942±0.06 g/cm3(Predicted)
• 保留指数：
  1465.1

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  5,5-dimethylcyclopent-2-enone 在 rhodium(II) acetate dimer 盐酸 、 sodium hydride 、 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 27.0h， 生成 蕨素 Z
  参考文献：
  名称：

  Generation and Cycloaddition Behavior of Spirocyclic Carbonyl Ylides. Application to the Synthesis of the Pterosin Family of Sesquiterpenes

  摘要：

  The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane and ethyl 3-(1-acetyl-cyclopropyl)-2-diazo-3-oxopropiolate with various dipolarophiles afforded dipolar cycloadducts in good yield. The reaction involves the formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMO considerations. For carbonyl ylides, the HOMO dipole is dominant for reactions with electron deficient dipolarophiles, while the LUMO becomes important for cycloaddition to more electron rich species. A short synthesis of several members of the pterosin family of sesquiterpenes is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide. The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)-cyclopropane with cyclopentenone afforded a dipolar cycloadduct in good yield as a 4:1 mixture of diastereomers. Treatment of the major cycloadduct with triphenylphosphonium bromide in the presence of sodium hydride gave the expected Wittig product. The reaction of this compound with acid in the presence of various solvents gave rise to several members of the pterosin family. The overall sequence of reactions can best be described as proceeding by an initial oxy-bridge ring opening followed by dehydration and a subsequent acid-catalyzed cyclopropyl ring opening. The facility of the process is undoubtedly related to the aromaticity gained in the final step.

  DOI：

  10.1021/jo951371e
• 作为产物：
  描述：

  1-甲基-2-氧代环戊烷-1-羧酸乙酯 在 chromium(VI) oxide 、 硫酸 作用下， 以 丙酮 为溶剂， 生成 5,5-dimethylcyclopent-2-enone
  参考文献：
  名称：

  用于 Illudin M 和 S 的 5,5-Dimethyl-4-acetoxy-2-cyclopentenone 和 5-Methyl-t-5-acetoxymethyl-r-4-acetoxy-2-cyclopentenone 中间体的合成

  摘要：

  5,5-二甲基-4-乙酰氧基-2-环戊烯酮和 5-甲基-t-5-乙酰氧基甲基-r-4-乙酰氧基-2-环戊烯酮分别是伊卢丁 M 和 S 的中间体，已由己二酸乙酯合成。

  DOI：

  10.1246/bcsj.45.1140

文献信息

• Aldosterone Synthase Inhibitor
  申请人：Bell Michael Gregory

  公开号：US20120322841A1

  公开（公告）日：2012-12-20

  The present invention provides aldosterone synthase inhibitors of the formula: intermediates, methods for their preparation, pharmaceutical preparations, and methods for their use.

  这项发明提供了以下结构的醛固酮合成酶抑制剂： 中间体，其制备方法，药物制剂以及使用方法。
• Cyclocarbonylation of acyclic 1,3-dienes via their tricarbonyl iron complexes : Cyclopenten-2-ones and dicarbonyl cyclopentadienyl iron halides
  作者：Michel Franck-Neumann、Enrique Luis Michelotti、Roland Simler、Jean-Michel Vernier

  DOI：10.1016/s0040-4039(00)60188-0

  日期：1992.11

  of acyclic 1,3-dienes can be converted to conjugated cyclopentenones by decomplexation with aluminium halides. Most complexes of a simple dienes need drastic conditions for the cyclocarbonylation to occur (100 Atm CO, 1000° C), with the exception of 1,1,3-trialkylbutadiene complexes which are nearly quantitatively converted into cyclopentenones at room temperature, even in the absence of a CO atmosphere

  无环1，3-二烯的三羰基铁配合物可通过与卤化铝解络而转化为共轭的环戊烯酮。大多数简单的二烯络合物都需要苛刻的条件才能发生环羰基化反应（100 Atm CO，1000°C），除了1,1,3-三烷基丁二烯络合物几乎可以在室温下定量转化为环戊烯，即使在室温下也是如此。没有CO气氛。在相同的温和条件下，其他配合物通过环羰基化反应以中等收率生成环戊二烯基二羰基卤化铁，然后通过卤化铝促进脱氧。
• [EN] ACYL BICYCLIX DERIVATIVES OF PYRROL<br/>[FR] DERIVES ACYLE BICYCLIQUES DE PYRROL
  申请人：GLAXO GROUP LTD

  公开号：WO2003097646A1

  公开（公告）日：2003-11-27

  The invention relates to anti-viral agents of Formula (I); wherein: RA represents OR1, NR1R2, or R1 wherein R1 and R2 independently represent hydrogen, C1-6alkyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl; or R1 and R2 together with the nitrogen atom to which they are attached form a 5 or 6 membered saturated cyclic group; RB represents C(O)R3 wherein R3 represents aryl or heteroaryl; RC represents C1-6alkyl, aryl, heteroaryl or heterocyclyl; RD represents hydrogen and RE represents hydrogen, OR4 or SR4, or RD and RE together with the carbon atom to which they are attached form a carbonyl group or a thiocarbonyl group; when RE is hydrogen, OR4 or SR4, RG and RH are both hydrogen; when RD and RE together with the carbon atom to which they are attached form a carbonyl group or a thiocarbonyl group, RG represents hydrogen and RH represents hydrogen, OR4 or SR4, or RG and RH together with the carbon atom to which they are attached form a carbonyl group or a thiocarbonyl group; R4 represents hydrogen, C1-6alkyl or aryl; when RD and RE together with the carbon atom to which they are attached form a carbonyl group or a thiocarbonyl group, and RG and RH are both hydrogen or RG and RH together with the carbon atom to which they are attached form a carbonyl group or a thiocarbonyl group, then RF represents O, S, NR5 or CR6R7, otherwise RF represents CR6R7; R5 represents hydrogen, C1-6alkyl, arylalkyl or aryl;R6 and R7 independently represent hydrogen, C1-6alkyl, arylalkyl or heteroarylalkyl;RJ represents hydrogen, C1-6alkyl, heterocyclylalkyl, arylalkyl or heteroarylalkyl; and salts, solvates and enantiomers thereof;provided that when RA is OR1 then R1 is other than tert-butyl, for use in medical therapy. A process for the preparation of compounds of Formula (I) and methods of using them in HCV treatment are provided.

  该发明涉及式(I)的抗病毒剂；其中：RA代表OR1，NR1R2或R1，其中R1和R2独立地代表氢，C1-6烷基，芳基，杂环芳基，芳基烷基或杂环芳基；或者R1和R2与它们连接的氮原子一起形成5或6成员饱和环状基团；RB代表C(O)R3，其中R3代表芳基或杂环芳基；RC代表C1-6烷基，芳基，杂环芳基或杂环烷基；RD代表氢，RE代表氢，OR4或SR4，或者RD和RE与它们连接的碳原子一起形成羰基团或硫代羰基团；当RE为氢，OR4或SR4时，RG和RH都是氢；当RD和RE与它们连接的碳原子一起形成羰基团或硫代羰基团时，RG代表氢，RH代表氢，OR4或SR4，或者RG和RH与它们连接的碳原子一起形成羰基团或硫代羰基团；R4代表氢，C1-6烷基或芳基；当RD和RE与它们连接的碳原子一起形成羰基团或硫代羰基团，且RG和RH都是氢或RG和RH与它们连接的碳原子一起形成羰基团或硫代羰基团时，RF代表O，S，NR5或CR6R7，否则RF代表CR6R7；R5代表氢，C1-6烷基，芳基烷基或芳基；R6和R7独立地代表氢，C1-6烷基，芳基烷基或杂环芳基烷基；RJ代表氢，C1-6烷基，杂环烷基，芳基烷基或杂环芳基烷基；以及其盐，溶剂合物和对映体；但是当RA为OR1时，R1不是叔丁基，用于医疗治疗。提供了一种制备式(I)化合物的方法以及在HCV治疗中使用它们的方法。
• Auto-tandem catalysis: facile synthesis of substituted alkylidenecyclohexanones by domino (4+2) cycloaddition–elimination reaction
  作者：Kiyosei Takasu、Toru Tanaka、Takumi Azuma、Yoshiji Takemoto

  DOI：10.1039/c0cc03336g

  日期：——

  2-alkylidenecyclohexanone from 3-oxymethyl-2-siloxy-1,3-butadienes, which can be prepared from Baylis-Hillman adducts, and alpha,beta-unsaturated ketones is described. The process involves two mechanistically distinct reactions, (4+2) cycloaddition and elimination. Both of these reactions are catalyzed by Tf(2)NH.

  描述了由3-氧甲基-2-甲硅烷氧基-1，3-丁二烯产生的取代的2-亚烷基环己酮的催化多米诺反应，其可以由Baylis-Hillman加合物和α，β-不饱和酮制得。该过程涉及两个机械上不同的反应，（4 + 2）环加成和消除。这两个反应都是由Tf（2）NH催化的。
• Sequential Intramolecular Cyclobutadiene Cycloaddition, Ring-Opening Metathesis, and Cope Rearrangement:  Total Syntheses of (+)- and (−)-Asteriscanolide
  作者：John Limanto、Marc L. Snapper

  DOI：10.1021/ja001946b

  日期：2000.8.23

  The value of new transformations can become apparent when brought to bear in complex molecule synthesis. To demonstrate the utility of intramolecular cyclobutadiene cycloadditions 1 and ring-opening metatheses, 2 we report herein the first application of these complementary transformations in the total syntheses of (+)and (-)-asteriscanolide ( 1). The incorporation of these reactions into the synthesis

  在复杂的分子合成中，新转化的价值会变得显而易见。为了证明分子内环丁二烯环加成 1 和开环复分解反应 2 的效用，我们在此报告了这些互补转化在 (+) 和 (-)-asteriscanolide 的全合成中的首次应用 (1)。将这些反应结合到 asteriscanolide 的合成中为天然产物提供了九步路线（最长的线性序列）。关键的合成断开如方案 1 所示。自 15 多年前发现以来，1 的新型倍半萜内酯环系统 3 引起了合成界的广泛关注。4 特别是，Krafft 和 Paquette 实验室报告了 asteriscanolide 的成功合成。5 然而，在这些最近的贡献之前，是 Wender、Ihle 和 Correia 对 1 的第一个也是迄今为止最短的综合。6 Wender 策略的中心是 Ni(0) 催化的分子内 [4 + 4] 环加成反应高度官能化的双 1,3-二烯，以提供含环辛二烯的中间体