[(2-methylphenyl)(methoxy)methylene]pentacarbonylchromium(0)

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(2-methylphenyl)(methoxy)methylene]pentacarbonylchromium(0)
• 英文别名: pentacarbonyl[(2-methylphenyl)(methoxy)carbene]chromium(0)；(CO)5CrC(C6H4CH3-o)OCH3
• 化学式: C₁₄H₁₀CrO₆
• 分子量: 326.226
• InChiKey: FJSLIYHHSFLTOU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  2-苯基吡啶 、 [(2-methylphenyl)(methoxy)methylene]pentacarbonylchromium(0) 以 甲苯 为溶剂， 反应 10.0h， 以66%的产率得到2-(2-(methoxy(o-tolyl)methyl)phenyl)pyridine
  参考文献：
  名称：

  通过氧化氢迁移与 Cr(0) Fischer Carbene 配合物进行氮杂环导向的正式芳烃 C(sp2)-H 插入

  摘要：

  报道了在无催化剂条件下氮杂环导向的分子间芳香族 C(sp 2 )–H 官能化的 Cr(0) Fischer 卡宾配合物。具有吡啶、嘧啶和吡唑作为导向基团的芳烃与铬 (0) 卡宾配合物以良好的产率和出色的区域选择性反应。根据基于密度泛函理论（DFT）的实验和计算的机理研究，该反应通过氧化氢迁移和还原消除遵循非常规机制，这与经典的亲电取代机制不同。

  DOI：

  10.1021/acs.organomet.1c00352
• 作为产物：
  描述：

  2-溴甲苯 、 六羰基铬 在 叔丁基锂 、 trimethoxonium tetrafluoroborate 作用下， 以 乙醚 、 正己烷 为溶剂， 以62%的产率得到[(2-methylphenyl)(methoxy)methylene]pentacarbonylchromium(0)
  参考文献：
  名称：

  Substrate regulation of product distribution in the reactions of arylchromium carbene complexes with alkynes

  摘要：

  The reactions of arylcarbene complexes with alkynes were examined for six of the nine possible substitution patterns for mono- and dioxygenated aryl substituents of the carbene carbon. The product distributions were found to be highly dependent on a number of factors, including solvent, temperature, concentration of alkyne, and the nature of the aryl substituent. The product distributions were determined in nearly all cases for phenol and indene products and in some cases for furans, cyclobutenones, and cyclopentenediones, which were minor products in these reactions. The product distribution for the reaction of each arylcarbene complex was determined as a function of both temperature and alkyne concentration, since the combined product distribution profiles provided a much more sensitive measure of the relative influences of the aryl substituents on the reaction outcome. Furthermore, this distribution profile was determined for the reactions with 3-hexyne and I-pentyne for each carbene complex. A series of monosubstituted arylcarbene complexes were examined to identify the effects of oxygen substituents at various positions on the aryl ring. The m-methoxy group has no effect on the product distribution, whereas the o-methoxy group influences the distribution by its ability to chelate to the metal center and the p-methoxy group influences the distribution by its ability to donate electrons by resonance. The product distributions from the reactions of the 2,3-, 2,4-, and 2,5-dimethoxy complexes followed the profile expected from the simple sum of the profiles of the monomethoxyl complexes. In all cases where an effect was observed, higher concentrations of alkyne led to a higher selectivity for phenol over indene products. The dependence of the product distribution on the concentration of the alkyne substrate is suggested to be due to a process in which a second molecule of alkyne coordinates to the metal center and determines the chemical outcome of an intermediate that has covalently incorporated the first alkyne. It is further suggested that the special ability of an alkyne to display this effect is related to the ability of an alkyne to readily switch from a 2 to a 4 e- donor. This phenomenon of substrate regulation of product distribution is termed the allochemical effect, and a mechanistic explanation is developed that features this proposed process and that is refined to accommodate the observed effects of solvent, temperature, chelation, and steric and electronic effects that have been observed for the reaction of carbene complexes and alkynes.

  DOI：

  10.1021/ja00024a040

文献信息

• 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。
• C–H Bond Functionalization of Benzoxazoles with Chromium(0) Fischer Carbene Complexes
  作者：Fangdong Hu、Jinghui Yang、Ying Xia、Chen Ma、Haiping Xia、Yan Zhang、Jianbo Wang

  DOI：10.1021/acs.organomet.6b00008

  日期：2016.5.23

  An efficient C-H bond functionalization of benzoxazoles with chromium(0) Fischer carbene complexes under catalyst-free conditions has been developed. A series of benzoxazoles and chromium(0) carbene complexes are compatible with the reaction. This transformation provides an alternative way for C-H bond alkylation of benzoxazoles. In the reaction mechanism the elimination of the Cr(CO)(5) fragment seems more favored than the elimination of an alkoxy group, which is in sharp contrast to the previous reports on the reaction of organolithium reagents with chromium(0) Fischer carbene complexes.
• Optically Active (<i>aR</i>)- and (<i>aS</i>)-Linear and Vaulted Biaryl Ligands: Deracemization versus Oxidative Dimerization
  作者：Gang Hu、Daniel Holmes、Brina Fay Gendhar、William D. Wulff

  DOI：10.1021/ja903820m

  日期：2009.10.14

  The copper-mediated deracemization of the C2-symmetric vaulted biaryl ligands VANOL and VAPOL has been investigated. In the course of the studies that have led to a more reliable procedure for this process, an unprecedented oxidative dimerization of these ligands has been uncovered. The structures of these oxidative dimerization products were elucidated by a series of NMR experiments, and these assignments were supported by other spectroscopic techniques as well as their chemical reactivity. This oxidative dimerization process was not observed for the linear biaryl ligands BANOL and BINOL, although the new deracemization procedure was effective for the generation of BINOL with high optical purity. The (aS)-enantiomers of BINOL, VANOL and VAPOL were accessible with a copper complex of (-)-sparteine, and the (aR)-enantiomeric series were accessible with a copper complex of O'Brien's diamine. Both sparteine and O'Brien's diamine give higher optical purities with VANOL and VAPOL than with BINOL, and this is consistent with the steric congestion present in the matched and mismatched copper complexes of these diamines with the biaryl ligands.
• Substrate regulation of product distribution in the reactions of arylchromium carbene complexes with alkynes
  作者：Mary Ellen Bos、William D. Wulff、Ross A. Miller、Steven Chamberlin、Timothy A. Brandvold

  DOI：10.1021/ja00024a040

  日期：1991.11

  The reactions of arylcarbene complexes with alkynes were examined for six of the nine possible substitution patterns for mono- and dioxygenated aryl substituents of the carbene carbon. The product distributions were found to be highly dependent on a number of factors, including solvent, temperature, concentration of alkyne, and the nature of the aryl substituent. The product distributions were determined in nearly all cases for phenol and indene products and in some cases for furans, cyclobutenones, and cyclopentenediones, which were minor products in these reactions. The product distribution for the reaction of each arylcarbene complex was determined as a function of both temperature and alkyne concentration, since the combined product distribution profiles provided a much more sensitive measure of the relative influences of the aryl substituents on the reaction outcome. Furthermore, this distribution profile was determined for the reactions with 3-hexyne and I-pentyne for each carbene complex. A series of monosubstituted arylcarbene complexes were examined to identify the effects of oxygen substituents at various positions on the aryl ring. The m-methoxy group has no effect on the product distribution, whereas the o-methoxy group influences the distribution by its ability to chelate to the metal center and the p-methoxy group influences the distribution by its ability to donate electrons by resonance. The product distributions from the reactions of the 2,3-, 2,4-, and 2,5-dimethoxy complexes followed the profile expected from the simple sum of the profiles of the monomethoxyl complexes. In all cases where an effect was observed, higher concentrations of alkyne led to a higher selectivity for phenol over indene products. The dependence of the product distribution on the concentration of the alkyne substrate is suggested to be due to a process in which a second molecule of alkyne coordinates to the metal center and determines the chemical outcome of an intermediate that has covalently incorporated the first alkyne. It is further suggested that the special ability of an alkyne to display this effect is related to the ability of an alkyne to readily switch from a 2 to a 4 e- donor. This phenomenon of substrate regulation of product distribution is termed the allochemical effect, and a mechanistic explanation is developed that features this proposed process and that is refined to accommodate the observed effects of solvent, temperature, chelation, and steric and electronic effects that have been observed for the reaction of carbene complexes and alkynes.
• Azacycle-Directed Formal Aromatic C(sp²)–H Insertion with Cr(0) Fischer Carbene Complex via Oxidative Hydrogen Migration
  作者：Xing-Qi Yao、Wen-Yan Tong、Kang Wang、Shuanglin Qu、Jianbo Wang

  DOI：10.1021/acs.organomet.1c00352

  日期：2021.11.8

  An azacycle-directed intermolecular aromatic C(sp2)–H functionalization of Cr(0) Fischer carbene complexes under catalyst-free conditions is reported. Arenes with pyridines, pyrimidine, and pyrazole as directing groups reacted with chromium(0) carbene complexes in good yields and excellent regioselectivities. According to the mechanistic studies based on experiments and computations with density functional

  报道了在无催化剂条件下氮杂环导向的分子间芳香族 C(sp 2 )–H 官能化的 Cr(0) Fischer 卡宾配合物。具有吡啶、嘧啶和吡唑作为导向基团的芳烃与铬 (0) 卡宾配合物以良好的产率和出色的区域选择性反应。根据基于密度泛函理论（DFT）的实验和计算的机理研究，该反应通过氧化氢迁移和还原消除遵循非常规机制，这与经典的亲电取代机制不同。