五羰基(1-甲氧基亚乙基)-铬 | 20540-69-6

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 中文名称: 五羰基(1-甲氧基亚乙基)-铬
• 英文名称: pentacarbonyl(methoxymethylcarbene)chromium(0)
• 英文别名: Pentacarbonylchrom；[(methyl)(methoxy)carbene]pentacarbonyl chromium(0)；[(CO)5CrC(OMe)(Me)]；(methoxy(methyl)carbene)pentacarbonylchromium(0)；(CO)5Cr((methoxy)(methyl)carbene)；pentacarbonyl(methoxymethyl)chromium(0) carbene；pentacarbonyl[(methyl)methoxymethylene]chromium；pentacarbonyl(methylmethoxycarbene)chromium(0)；pentacarbonyl[methoxy(methyl)carbene]chromium；(CO)5Cr(methylmethoxycarbene)；pentacarbonyl-(1-methoxy-ethylidene)-chromium；Cr(C(OMe)Me)(CO)5；Cr(CO)5(C(Me)OMe)
• CAS: 20540-69-6
• 化学式: C₈H₆CrO₆
• 分子量: 250.128
• InChiKey: LTUCUZGOLBLHGU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.14
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  14.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  五羰基(1-甲氧基亚乙基)-铬 以 乙醚 为溶剂， 生成 Carbon monoxide;chromium;prop-2-enenitrile
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cr: Org.Verb., 1.1.2.1.4.1, page 41 - 54

  摘要：

  DOI：
• 作为产物：
  描述：

  五羰基[氨基(甲基)卡宾]铬(0) 在 Na 作用下， 以 乙醚 为溶剂， 生成 五羰基(1-甲氧基亚乙基)-铬
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cr: Org.Verb., 1.1.2.3.3.1, page 106 - 112

  摘要：

  DOI：
• 作为试剂：
  描述：

  S,S-dimethyl-N-(p-anisyl)sulfilimine 在 氧气 、 五羰基(1-甲氧基亚乙基)-铬 作用下， 以90%的产率得到methyl α-(p-anisidinyimino acetate)
  参考文献：
  名称：

  Reaction of chromium (Fischer) carbenes and sulfilimines

  摘要：

  The photochemical reactions of alkoxychromium (Fischer) carbenes and sulfilimines lead to imidates in fair to excellent yields. Aromatic, heteroaromatic, and alkylsulfilimines, the latter bearing functional groups such as cyano, sulfone, ether, ester, and dioxolane groups, gave the corresponding imidates in good to excellent yield. However, acyl- and sulfonyl-substituted sulfilimines did not react with chromium carbenes, except for sulfilimines bearing ethoxycarbonyl and phtalimidylamino groups. A variety of differently substituted chromium carbene complexes bearing alkyl, cycloalkyl, styryl, allyl, and alkynyl groups attached either at the carbene carbon or at the oxygen also gave imidates in good yields. For alpha,beta-unsaturated carbenes, the exclusive 1,2-addition of the sulfilimine nitrogen was observed at room temperature, in contrast to the behavior of other nitrogen nucleophiles which are reported to add in 1,4-fashion under these reaction conditions. In turn, optically active imidates of the type ArN=C(OR*)Me [R* = chiral substituent derived from (R)-(+)-1-phenyl-1-butanol, l-(-)-menthol, (1S)-endo-(-)-borneol, and (1R)-(-)-myrtenol] can be prepared efficiently by utilizing the corresponding chiral alkoxy group on the earbene moiety. The reactions above also occur in the dark but reaction times are considerably longer. N-Halosulfilimines reacted with alkoxychromium carbenes to yield N-acylsulfilimines instead of the expected N-haloimidates. Based upon a set of thermal and photochemical reactions between N-haloimidates and diphenyl sulfide in the absence of chromium complexes, the complex (CO)5CrNCMe is proposed to be responsible for this novel reaction of N-haloimidates and diphenyl sulfide.

  DOI：

  10.1021/jo00067a020

文献信息

• Synthesis of chromium N-heterocyclic carbene complexes using chromium Fischer carbenes as a source of chromium carbonyls
  作者：Seongjin Kim、Soo Young Choi、Young Tak Lee、Kang Hyun Park、Helmut Sitzmann、Young Keun Chung

  DOI：10.1016/j.jorganchem.2007.08.043

  日期：2007.11

  Chromium Fischer carbene complexes, [CrOMe(R)}(CO)5] have been utilized as a source of chromium carbonyls in the synthesis of chromium NHC complexes. Using the synthetic method, chromium complexes of various NHC ligands were isolated in reasonable yields. Moreover, the method can be employed for the synthesis of molybdenum and tungsten NHC compounds.

  铬费歇尔卡宾络合物[Cr OMe（R）}（CO）5 ]已被用作铬NHC络合物的合成中的羰基铬源。使用合成方法，可以合理的产率分离出各种NHC配体的铬配合物。此外，该方法可用于合成钼和钨NHC化合物。
• Synthesis of Naphthalenes through Three-Component Coupling of Alkynes, Fischer Carbene Complexes, and Benzaldehyde Hydrazones via Isoindole Intermediates
  作者：Shaofeng Duan、Dilip K. Sinha-Mahapatra, and、James W. Herndon

  DOI：10.1021/ol800242n

  日期：2008.4.1

  The synthesis of naphthalene derivatives through three-component coupling of 2-alkynylbenzaldehyde hydrazones with carbene complexes and electron-deficient alkynes has been examined. The reaction involves formation of an isoindole derivative, followed by intramolecular Diels-Alder reaction, followed by nitrene extrusion. The reaction was highly regioselective using unsymmetrical alkynes.

  已经研究了通过 2-炔基苯甲醛腙与卡宾配合物和缺电子炔烃的三组分偶联合成萘衍生物。该反应包括形成异吲哚衍生物，然后是分子内 Diels-Alder 反应，然后是氮烯挤出。该反应使用不对称炔烃具有高度区域选择性。
• The course of the reaction of azobenzene with chromium carbene complexes
  作者：Louis S. Hegedus、Bruce R. Lundmark

  DOI：10.1021/ja00208a010

  日期：1989.12

  La reaction entre le cis-azobenzene et le pentacarbonyle([methoxy methyl] methylene)chrome (0) fait intervenir un intermediaire zwitterionique et un intermediaire metallocycle, qui ont pu etre detectes

  La 反应 entre le cis-azobenzo et le pentacarbonyle([甲氧基甲基] 亚甲基)chrome (0) fait intervenir un intermediaire zwitterionique et un intermediaire metallocycle, qui ont pu etre detectiones
• New Method for the Preparation of Alkoxycarbene Complexes of Chromium, Molybdenum, and Tungsten Using Sulfonium Salts
  作者：Takako Nakamura、Haruo Matsuyama、Masahiko Iyoda

  DOI：10.1246/cl.1994.1537

  日期：1994.8

  Alkylation of tetramethylammonium acylate complexes of chromium, molybdenum, and tungsten with alkyldiphenylsulfonium salts readily proceeds under mild conditions to afford alkoxycarbene complexes containing a variety of functional groups in good yields.

  铬、钼和钨的四甲基酰化铵配合物与烷基二苯基锍盐的烷基化反应在温和条件下很容易进行，以良好的产率得到含有多种官能团的烷氧基卡宾配合物。
• Pd-catalyzed Oxidative Cross-coupling of Alkyl Chromium(0) Fischer Carbene Complexes with Organoboronic Acids
  作者：Kang Wang、Jinghui Yang、Xingqi Yao、Jianbo Wang

  DOI：10.1002/asia.201801278

  日期：2018.11.2

  Alkyl chromium(0) carbene complexes have been explored as the cross‐coupling partners in the palladium‐catalyzed reaction with aryl or alkenyl boronic acids. This coupling reaction displays the versatile reactivities of alkyl chromium(0) carbenes under palladium catalysis. Mechanistically, this transformation is proposed to involve deprotonation of the alkyl chromium carbene substrate to generate a

  烷基铬（0）卡宾配合物已被探索为钯与芳基或烯基硼酸催化的交叉偶联伙伴。此偶联反应显示了钯催化下烷基铬（0）卡宾的通用反应性。从机理上讲，提出这种转变涉及烷基铬卡宾底物的去质子化以产生乙烯基铬阴离子中间体，该中间体经历金属转移成有机钯物质并还原消除。