((dihydro-2-pyranyl)methoxymethylene)pentacarbonyltungsten

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环化合物
• 英文名称: ((dihydro-2-pyranyl)methoxymethylene)pentacarbonyltungsten
• 英文别名: carbon monoxide;[3,4-dihydro-2H-pyran-6-yl(methoxy)methylidene]tungsten
• 化学式: C₁₂H₁₀O₇W
• 分子量: 450.057
• InChiKey: IDTFFUYZIDGRCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.82
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  23.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ((dihydro-2-pyranyl)methoxymethylene)pentacarbonyltungsten 、 lithium 1-phenylethenolate 在 碘 作用下， 以 四氢呋喃 为溶剂， 以78%的产率得到
  参考文献：
  名称：

  从 Fischer Carbene 配合物合成功能化 1,3-丁二烯和环戊烯酮的简单程序

  摘要：

  用衍生自甲基酮和碘的烯醇锂对烯基卡宾配合物进行连续处理会产生含有给电子和吸电子基团的官能化 1,3-丁二烯衍生物。通过用烯醇锂、碘和催化量的三氟甲磺酸铜 (II) 顺序处理二氢吡喃卡宾配合物，可以轻松获得功能化的双环环戊烯酮。

  DOI：

  10.1055/s-2006-949612
• 作为产物：
  描述：

  3,4-二氢-2H-吡喃 、 六羰基钨 、 trimethoxonium tetrafluoroborate 在 t-BuLi 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 以53%的产率得到((dihydro-2-pyranyl)methoxymethylene)pentacarbonyltungsten
  参考文献：
  名称：

  第6组菲舍尔卡宾配合物与炔烃的反应：金属对产物分布的影响以及非互变异构化环己二酮配合物的分离

  摘要：

  The first comparative study on the effect of the nature of the metal on the reactions of unsaturated group 6 Fischer carbene complexes with alkynes is reported. The scope of the study includes both aryl- and alkenylcarbene complexes of chromium, molybdenum, and tungsten for both internal and terminal alkynes. Twenty-one different organic structural types have been isolated and characterized from these reactions, but in most instances phenols and indene (cyclopentadiene) products are the two most frequently observed. The general observation made is that phenol formation is favored over indene (cyclopentadiene) formation in the order chromium > tungsten > molybdenum. The effect of the concentration of the alkyne on the distribution between phenol and indene (cyclopentadiene) was also examined and was found to be most prevalent in the order molybdenum > chromium > tungsten. The bis(alkyne)(eta4-cyclohexadienone)molybdenum complex 107 has been isolated in which the final tautomerization to the phenol product has not occurred. This complex has been characterized by X-ray diffraction and provides support for the previous interpretations of the concentration effects for the reactions of chromium complexes. This complex is the first example of the long-proposed ultimate intermediate in these reactions. Crystal data for 107: space group P2(1)/c, Z = 4, a = 19.088(4) angstrom, b = 10.101(1) angstrom c = 14.578(3) angstrom, a = 90.0-degrees, beta = 109.917(13)-degrees, gamma = 90.0-degrees, R = 0.0598, and R(w) = 0.0788 for the 2405 reflections observed.

  DOI：

  10.1021/om00013a021

文献信息

• Higher-order cyclization reactions of alkenyl Fischer carbene complexes: a new selective all-carbon [8 + 2] cyclization with 8-methoxyheptafulvene and computational mechanistic analysis
  作者：Jaime García-Rodríguez、Jairo González、Javier Santamaría、Ángel L. Suárez-Sobrino、Miguel A. Rodríguez

  DOI：10.1039/c6dt01465h

  日期：——

  A new higher-order cyclization reaction of alkenyl Fischer carbene complexes is described. Chromium and tungsten alkenyl Fischer carbene complexes react toward 8-methoxyheptafulvene through an all-carbon formal [8 + 2] cycloaddition reaction with complete regio- and stereoselectivity. Tetrahydroazulene compounds bearing four consecutive stereocenters are generated. The reaction mechanism is rationalized

  描述了一种新的烯基菲舍尔卡宾配合物的高阶环化反应。铬和钨烯基菲舍尔卡宾络合物通过全碳的形式[8 + 2]环加成反应，向8-甲氧基庚烯富烯反应，具有完全的区域和立体选择性。产生带有四个连续的立体中心的四氢氮杂烯化合物。根据计算结果合理化反应机理。发现这种转变是通过协调的过程进行的。所观察到的立体选择性和区域选择性的性质可以归因于空间因素和电子因素。
• Diastereoselective Synthesis of Three-, Five-, Six-, and Seven-Membered Rings from Fischer Carbene Complexes and 4-Unsubstituted 1-Amino-1,3-Dienes
  作者：Fernando Aznar、Martín Fañanás-Mastral、Jorge Alonso、Francisco J. Fañanás

  DOI：10.1002/chem.200701109

  日期：2008.1

  Fischer carbene complexes react with 4-unsubstituted 1-amino-1,3-dienes to give different carbocyclization products depending on the nature of the carbene complex and on the substitution pattern of the aminodiene. Thus, the reaction of arylcarbene chromium complexes and 1-aminodienes diastereoselectively affords cyclopropane derivatives by means of a formal [2+1] carbocyclization reaction. In particular

  菲舍尔卡宾配合物与4-未取代的1-氨基-1,3-二烯反应，生成不同的碳环化产物，具体取决于卡宾配合物的性质和氨基二烯的取代方式。因此，芳基卡宾铬配合物和1-氨基二烯非对映选择性地反应，通过正式的[2 + 1]碳环化反应。特别是五羰基[（2-呋喃基）（甲氧基）亚甲基]铬配合物提供了正式的[4 + 1]碳环化产物。从β-取代的烯基卡宾配合物开始，发生正式的[4 + 1]反应，并且非对映选择性地形成环戊烯胺衍生物。但是，当使用α，β-二取代的烯基碳烯络合物五羰基[（5,6-二氢-2H-吡喃-2-基）（甲氧基）亚甲基]钨时，反应的结果取决于在氨基二烯的3位碳原子上的取代，如果取代基分别为氢原子或不是氢原子，则分别生成[3 + 2]或[4 + 3]-环化产物。最后，当用炔基卡宾配合物进行反应时，如果三键取代基为苯基，则获得苯甲醛衍生物；如果该基团为烯基部分，则获得茚衍生物。