pentacarbonyl[(methoxy)(2-methoxyphenyl)carbene]chromium(0)

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: pentacarbonyl[(methoxy)(2-methoxyphenyl)carbene]chromium(0)
• 英文别名: Pentacarbonyl{methoxy(methoxy-2-phenyl)carben}chrom；pentacarbonyl[(methoxy)(2-methoxyphenyl)carbene]chromium
• 化学式: C₁₄H₁₀CrO₇
• 分子量: 342.225
• InChiKey: WDYYWKVJFVJJEB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.18
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  pentacarbonyl[(methoxy)(2-methoxyphenyl)carbene]chromium(0) 在 potassium osmate(VI) dihydrate 、 草酰氯 、 甲基磺酰胺 、 四丁基氟化铵 、 sodium hydride 、 碳酸氢钠 、 potassium carbonate 、 二甲基亚砜 、 氢化奎宁 1,4-(2,3-二氮杂萘)二醚 、 三乙胺 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 69.17h， 生成 (4S,5S)-4-hydroxy-5-(1',4',5'-trimethoxynaphth-2'-yl)dihydrofuran-2(3H)-one
  参考文献：
  名称：

  A Dötz benzannulation route to the enantioselective synthesis of (−)- and (+)-juglomycin A

  摘要：

  Two synthetic routes based on a Dotz benzannulation toward the enantioselective synthesis of naphthoquinone antibiotics (-)- and (+)-juglomycin A are described. The stereoinducing step is based on asymmetric dihydroxylation. The syntheses are completed in seven to eight steps from Fischer carbene 12. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.07.018
• 作为产物：
  描述：

  六羰基铬 以80%的产率得到
  参考文献：
  名称：

  WULFF, WILLIAM D.;XU, YAO-CHANG, J. AMER. CHEM. SOC., 110,(1988) N 7, 2312-2314

  摘要：

  DOI：
• 作为试剂：
  描述：

  1-苯基-1-丙炔 在 ammonium cerium(IV) nitrate 、 pentacarbonyl[(methoxy)(2-methoxyphenyl)carbene]chromium(0) 作用下， 生成 2-Methyl-3-phenyl-5-methoxy-1,4-naphthalenedione 、 1,7-Dimethoxy-2-methyl-3-phenyl-1H-indene 、 1,7-Dimethoxy-3-methyl-2-phenyl-1H-indene 、 7-Methoxy-3-methyl-2-phenyl-inden-1-one 、 7-Methoxy-2-methyl-3-phenyl-inden-1-one 、 5-Methoxy-3-methyl-2-phenyl-[1,4]naphthoquinone
  参考文献：
  名称：

  Mechanistic Studies on the Reaction of Fischer Carbene Complex with Alkynes:  Does the Alkyne Insertion Intermediate Form Irreversibly?

  摘要：

  The regioselectivity of the formation of three different products from the reaction of 1-phenylpropyne with (methoxy)(2-methoxyl-1-phenyl)methylene pentacarbonyl chromium 12 was examined in detail. The phenol product is formed with a substantial regioselectivity which is temperature-dependent, but the indene products (obtained as two compounds: indene and indenone) are formed as a nearly equal mixture of regioisomers. The proportion of indene and phenol products is dependent on the concentration with greater amounts of phenol products being formed at higher concentrations. The total regioselectivity of all of the products is also a function of the concentration. This result could be due either to an equilibration of the eta(1),eta(3)-vinyl carbene intermediates in this reaction or to a change in mechanisms in the formation of the eta(1),eta(3)-vinyl carbene intermediated from one involving a dissociative incorporation of the alkyne to one involving an associative incorporation of the alkyne. Kinetic studies reveal that at 45 degrees C and at 0.5 M (but not 0.0001 M) the reaction is bimolecular with a first-order dependence on both the carbene complex and the alkyne. However, at 90 degrees C the reaction is first-order in carbene complex and zero-order in alkyne over the concentration range of 0.05-0.005 M where the total regioselectivity changes from 2.5:1.0 to 1.5:1. This observation constitutes the first experimental evidence for the equilibration of regioisomeric vinyl carbene intermediates during the benzannulation reaction. This equilibration could occur as a result of a deinsertion of the alkyne or via a cyclopropene intermediate. Finally the generality of the unprecedented bimolecular reaction of complex 12 with 1-phenylpropyne at high concentrations was examined for the reaction methoxy(phenyl)methylene pentacarbonyl chromium 28 with diphenylacetylene and phenylacetylene at 0.5 M, and it was found that both reactions are first-order in carbene complex only.

  DOI：

  10.1021/ja983101u

文献信息

• Fischer Carbene Pentannulation with Alkynes Having Adjacent Carbonate or Acyloxy Groups: Synthesis of 3-Substituted 1-Indanones
  作者：Rodney A. Fernandes、Sachin P. Gholap、Vijay P. Chavan、Akeel S. Saiyed、Shubhankar Bhattacharyya

  DOI：10.1021/acs.orglett.0c00901

  日期：2020.5.1

  Various aryl Fischer carbenes reacted with alkynes having adjacent acyloxy or carbonate groups to regioselectively deliver 3-substituted 1-indanones. The acyloxy or carbonate group probably coordinates with the Cr metal to give a tetra-coordinated chromium complex forming a six-membered ring that retards CO insertion for ketene formation, which is required for benzannulation. Alternatively, the ortho

  各种芳基菲舍尔卡宾烯与具有相邻酰氧基或碳酸酯基团的炔反应，以区域选择性地递送3-取代的1-茚满酮。酰氧基或碳酸酯基团可能与Cr金属配位，得到四配位的铬络合物，形成六元环，该环阻碍了烯键形成所需的CO插入乙烯酮。可选地，邻位芳基环的进攻导致戊环化，从而提供区域选择性的3-取代的1-茚满酮。该方法扩展到3-表位-异泛醇的核心结构的合成。
• Reaction of complex ligands: Part 95. Chromium tricarbonyl complexes of polysubstituted naphthohydroquinones: regioselective synthesis via [3+2+1]-benzannulation and haptotropic rearrangement
  作者：Karl Heinz Dötz、Normen Szesni、Martin Nieger、Kalle Nättinen

  DOI：10.1016/s0022-328x(03)00045-7

  日期：2003.4

  A series of polysubstituted naphthohydroquinoid tricarbonyl chromium complexes were prepared by chromium mediated [3+2+1]-benzannulation of Fischer-type carbene complexes with alkynes. The kinetics and the thermodynamic data of the η6-η6-haptotropic rearrangements were investigated by in-situ NMR spectroscopy. The free activation energies ΔG# range from 23 to 26 kcal mol−1 and only slightly depend

  铬介导的[3 + 2 + 1]-菲舍尔型卡宾配合物与炔烃的苯并[3 + 2 + 1]-苯甲酸酯化反应制备了一系列多取代的萘​​氢醌类三羰基铬配合物。动力学和η的热力学数据6 -η 6个-haptotropic重排通过原位NMR光谱研究。自由活化能ΔG ＃的范围为23至26 kcal mol -1并且仅略微取决于替代物的体积和供体/受体的性质。对于在非羟基喹啉环（环A）上带有甲氧基取代基的萘氢醌复合物，观察到金属迁移的平衡。在环A上带有甲基或仅带有氢取代基的配合物中，触变重排是不可逆的。NMR研究表明，在六氟苯中薄荷氧基取代的三羰基铬络合物的重排发生在分子内。配合物19的两个非对映异构体显示出不同的金属位移速率常数，这是动力学数据的第一个实例，其在两个非对映异构化合物中ML n片段的重排不同。
• A four-step route to synthetic equivalents of ortho-xylylenes: Dötz benzannulation, desilylation, bromo-dehydroxylation, and sultine formation. A concise approach to oxygenated linearly fused polycyclic aromatics
  作者：Sambasivarao Kotha、Vikas R. Aswar、Amarender Manchoju

  DOI：10.1016/j.tet.2016.03.047

  日期：2016.5

  A new route has been reported for the synthesis of densely oxygenated polycyclic aromatic compounds via cycloaddition approach. This strategy involves the Dötz benzannulation and Diels-Alder reaction as key steps. Naphthalene synthons required here were generated by Dötz benzannulation between aryl chromium carbene complexes and symmetrical internal alkyne.

  已经报道了通过环加成法合成高氧合多环芳族化合物的新途径。该策略涉及Dötz苯环和Diels-Alder反应作为关键步骤。此处所需的萘合成子是通过芳族铬卡宾配合物和对称内部炔烃之间的Dötz苯并环生成的。
• Chromium-53 nuclear magnetic resonance studies of pentacarbonylchromium carbene complexes
  作者：Andreas. Hafner、Louis S. Hegedus、Guy. DeWeck、Bruce. Hawkins、Karl H. Doetz

  DOI：10.1021/ja00233a018

  日期：1988.12

  The sup 53}Cr NMR spectra of 46 chromium-carbene complexes were recorded, and chemical shift and line width data are reported, along with associated infrared, uv-visible, and sup 13}C NMR spectroscopic data. The sup 53}Cr chemical shifts correlated very well with the donor-acceptor properties of the carbene ligand and were quite sensitive to steric influences on efficiency of pi}-overlap of the

  记录了 46 种铬-卡宾配合物的 sup 53}Cr NMR 光谱，并报告了化学位移和线宽数据，以及相关的红外、紫外可见和 sup 13}C NMR 光谱数据。sup 53}Cr 化学位移与卡宾配体的供体-受体性质非常相关，并且对杂原子与卡宾碳的 pi} 重叠效率的空间影响非常敏感。delta}(sup 53}Cr) 与亚胺形成β}-内酰胺的反应性没有相关性，但线宽似乎与反应性有关。初步尝试利用sup 53}Cr NMR 数据来指导铬-卡宾配合物的合成利用。5 个参考文献，49 个图，1 个标签。
• Palladium-Catalyzed Reductive Cross-Coupling Reaction of Aryl Chromium(0) Fischer Carbene Complexes with Aryl Iodides
  作者：Kang Wang、Yu Lu、Fangdong Hu、Jinghui Yang、Yan Zhang、Zhi-Xiang Wang、Jianbo Wang

  DOI：10.1021/acs.organomet.7b00657

  日期：2018.1.8

  The first palladium-catalyzed reductive cross-couplings of aryl chromium(0) carbene complexes with aryl iodides have been realized. This coupling reaction shows excellent functional group tolerance and high efficiency. Mechanistically, aryl chromium(0) carbene complexes undergo transmetalation with arylpalladium species to generate palladium(II) carbene intermediates, which is followed by migratory

  已经实现了芳族铬（0）卡宾配合物与芳基碘化物的第一个钯催化的还原交叉偶联。该偶联反应显示出优异的官能团耐受性和高效率。从机理上讲，芳基铬（0）卡宾配合物与芳基钯物种进行金属转移生成钯（II）卡宾中间体，然后迁移插入。然后通过氢转移和还原消除完成催化循环。与机理假说一致，密度泛函理论（DFT）计算支持钯卡宾中间体的参与，卡宾迁移插入是一个容易的步骤，其能垒为5.1 kcal / mol。卡宾转移步骤和氢转移步骤被确认为催化循环中的限速步骤。