tricarbonyl[(2-5-η)-4-methoxycyclohexa-2,4-dienone]iron | 12307-09-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tricarbonyl[(2-5-η)-4-methoxycyclohexa-2,4-dienone]iron
• 英文别名: tricarbonyl-4-methoxycyclohexa-2,4-dien-1-oneiron；Carbon monoxide;iron;4-methoxycyclohexa-2,4-dien-1-one
• CAS: 12307-09-4；331472-63-0；331472-65-2
• 化学式: C₁₀H₈FeO₅
• 分子量: 264.018
• InChiKey: YGYOBDBKVFDBQS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.93
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  29.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tricarbonyl[(2-5-η)-4-methoxycyclohexa-2,4-dienone]iron 生成 carbon monoxide;ethyl (2E)-2-(4-methoxycyclohexa-2,4-dien-1-ylidene)acetate;iron
  参考文献：
  名称：

  STEPHENSON, G. RICHARD;VOYLE, MARTYN;WILLIAMS, SARAH, TETRAHEDRON LETT., 31,(1990) N8, C. 3979-3982

  摘要：

  DOI：
• 作为产物：
  描述：

  tricarbonyl[(1-4-η)-2-methoxy-5-methylenecyclohexa-1,3-diene]iron 、 臭氧 在 二甲基硫 作用下， 以 二氯甲烷 为溶剂， 以40%的产率得到tricarbonyl[(2-5-η)-4-methoxycyclohexa-2,4-dienone]iron
  参考文献：
  名称：

  1,3-Dipolar Cycloaddition to Tricarbonyl[(1−4-η)-2- methoxy-5-methylenecyclohexa-1,3-diene]iron:  Rapid Construction of a Spiro[4.5]decane System

  摘要：

  Tricarbonyl[(1-4-eta)-2-methoxy-5-methyl-enecyclohexa-1,3-diene]iron (1) undergoes 1,3-dipolar cycloaddition reaction regio-, stereo-, and chemoselectively at its exocyclic double bond, yielding a spiro[4.5]-decane system. Reactive 1,3-dipoles with low-lying LUMO's such as nitrile oxides, ozone, diazoacetate, and oxoallyl cation participate well in cycloaddition to give isoxazole, ketone, pyrazoline, and cyclopentanone adducts, respectively. The complex 1 can be viewed as the synthetic equivalent of synthon 2 and has been illustrated for the first time as a versatile synthetic intermediate.

  DOI：

  10.1021/om950770x

文献信息

• Organometallic compounds in organic synthesis. Part 10. Preparations and some reactions of tricarbonyl-1,3- and -1,4-dimethoxycyclohexa-1,3-dieneiron and related compounds: the preparation of the tricarbonyl-3-methoxycyclohexadienyliumiron cation
  作者：Arthur J. Birch、Lawrence F. Kelly、David J. Thompson

  DOI：10.1039/p19810001006

  日期：——

  Tricarbonylcyclohexadienyliumiron cations can be regarded as synthetic equivalents, depending on the reaction sequence, either of specific aryl cations or, in the case of methoxy-derivatives, of cations derived from cyclohex-2-enones. An important series can be entered through the symmetrical 3-methoxy cation (32, R1= R2= H, R3= OMe) made efficiently for the first time from tricarbonyl-1,3-dimethoxycyclohexa-1

  三羰基环己二烯基亚铁阳离子可被视作合成的等价物，具体取决于反应顺序，是特定的芳基阳离子，还是在甲氧基衍生物的情况下，衍生自环己-2-烯酮的阳离子。一个重要的系列可以通过对称的3-甲氧基阳离子输入（32，R 1 = R 2 = H，R 3 = OME）有效地进行从三羰基-1,3- dimethoxycyclohexa -1,3- dieneiron第一次（ 18）。它在合成上等效于一个meta-甲氧基-苯阳离子或环己-2-烯酮的5-阳离子。可以基于三羰基环己2,4-二烯酮铁（33）衍生物的1位亲核反应以及（33）及其3-甲氧基（35）和4-甲氧基的有效合成来定义另一系列芳族等同物（37）描述了派生词。这些反应的前体需要1,3-或1,4-二甲氧基环己二烯的有效络合，这可以使用发生OMe损失的共轭而非未共轭的1,4-二烯进行。在一些1-吗啉代环己-1,3-二烯的配合物的制备和使用中描述了相关的方法。讨论了一些机制。
• Fine-tuning electrophilicity of cationic tricarbonyliron complexes
  作者：Andrei V. Malkov、G.Richard Stephenson

  DOI：10.1016/0022-328x(94)05169-c

  日期：1995.3

  Solvent effects can be used to switch aryllithium addition to η5-cyclohexadienyl tricarbonyliron complexes between novel formation of an acyl product, and the synthetically more valuable direct addition to the dienyl ligand. This gives efficient access to o-functionalised 1-arylcyclohexadienyl complexes for use in alkaloid synthesis.

  溶剂效应可用于开关的芳基锂除了η 5 -cyclohexadienyl tricarbonyliron络合物新颖形成酰基的产品，和合成更有价值直接除了二烯基配位体之间。这使得可以有效地获得用于生物碱合成的o-官能化的1-芳基环己二烯基复合物。
• Addition of aryl substituents to cyclohexadienyliron electrophiles in the development of routes to C12 central building blocks for alkaloid synthesis
  作者：Andrej V Malkov、Audrey Auffrant、Christophe Renard、Eric Rose、Françoise Rose-Munch、David A Owen、Elizabeth J Sandoe、G Richard Stephenson

  DOI：10.1016/s0020-1693(99)00390-4

  日期：1999.12

  Novel iron-aroyl complexes or synthetically prized arylcyclohexadienyl complexes can be formed from tricarbonyl(eta(5)-1,4-dimethoxycyclohexadienyl)iron(1 +) hexafluorophosphate(1 -) by correct control of reaction sequences that exploit the addition of aryllithium reagents to introduce the aromatic group. Bimetallic products are obtained when a tricarbonylchromium-bound aryllithium reagent or the corresponding cuprate are employed. (C) 1999 Elsevier Science S.A. All rights reserved.
• BIRCH A. J.; KELLY L. F.; THOMPSON D. J., J. CHEM. SOC. PERKIN TRANS., 1981, 1, NO 4, 1006-1012
  作者：BIRCH A. J.、 KELLY L. F.、 THOMPSON D. J.

  DOI：——

  日期：——
• 1,3-Dipolar Cycloaddition to Tricarbonyl[(1−4-η)-2- methoxy-5-methylenecyclohexa-1,3-diene]iron:  Rapid Construction of a Spiro[4.5]decane System
  作者：Chi Wi Ong、Ting-Lin Chien

  DOI：10.1021/om950770x

  日期：1996.2.20

  Tricarbonyl[(1-4-eta)-2-methoxy-5-methyl-enecyclohexa-1,3-diene]iron (1) undergoes 1,3-dipolar cycloaddition reaction regio-, stereo-, and chemoselectively at its exocyclic double bond, yielding a spiro[4.5]-decane system. Reactive 1,3-dipoles with low-lying LUMO's such as nitrile oxides, ozone, diazoacetate, and oxoallyl cation participate well in cycloaddition to give isoxazole, ketone, pyrazoline, and cyclopentanone adducts, respectively. The complex 1 can be viewed as the synthetic equivalent of synthon 2 and has been illustrated for the first time as a versatile synthetic intermediate.