化复合物与Ph3SiO连接物是极其实用和耐受的基转化前催化剂和高效的转移剂
Martin Bindl1, Robert Stade, Eike K Heilmann
1Max-Planck-Institut fur Kohlenforschung, D-45470 Mulheim/Ruhr, Germany.
Journal of the American Chemical Society
|June 19, 2009
概括
新的化复合物在基基转化中表现出极好的催化活性. 一个复合体,体11,是稳定的空气和宽泛的功能性组耐受性,简化其在合成复杂分子的使用.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
背景情况:
- 基基因转化是有机合成中的关键反应.
- 现有的基基转化预催化剂往往缺乏稳定性或易于处理.
研究的目的:
- 开发用于基转基因的基于化的新型,稳定和高度活性的前催化剂.
- 评估这些新系统的催化性能和功能组耐受性.
主要方法:
- 在现场制备的化复合物[{Ph}{3}SiO) {3}Mo[三键]N] (10) 从[{Me}{3}SiO) {2}{Me}{3}Si) {2}N) {3}Mo[三键]N] (9) 和Ph{3}SiOH.
- 形成和分离的皮里丁添加物[pyridine]{pyridine}{Ph}{3}SiO){3}Mo[三键]N] (11) 的形成和分离.
- 在各种基转化反应中测试复合物10和11的催化活性.
主要成果:
- 复合物10及其胺添加物11在各种基因转化反应中表现出极好的催化活性.
- Adduct 11是稳定的空气和易于处理,超过现有的预催化剂在可用性.
- 催化系统显示了广泛的功能组兼容性,包括,胺和受保护的酒精.
- 成功合成生物活性天然产品的关键中间体,如epothilone A和latrunculin类似物.
结论:
- 新型化复合物,特别是稳定于空气的合物11,代表了基转化催化学的重大进步.
- 这些预催化剂提供了增强的稳定性,易于使用和广泛的基质范围,促进复杂有机分子的合成.
- 该系统与各种功能组的兼容性使其成为合成化学家的一种多功能工具.
更多相关视频
09:37Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
相关概念视频
Metal-Ligand Bonds
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Preparation of Nitriles
One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...
Nitriles to Amines: LiAlH4 Reduction
Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
Nitriles to Ketones: Grignard Reaction
Organomagnesium halides, commonly known as Grignard reagents, convert nitriles to ketones and proceed through a nucleophilic acyl substitution. Nitriles react with a Grignard reagent, followed by an aqueous acid, to yield ketones. The reaction introduces a new carbon–carbon bond. The alkyl–magnesium bond in the Grignard reagent is highly polar, so the alkyl carbon develops a carbanionic character and acts as a nucleophile.
The mechanism begins with a nucleophilic attack by the Grignard reagent...
The mechanism begins with a nucleophilic attack by the Grignard reagent...
Properties of Organometallic Compounds
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
Complexation Equilibria: The Chelate Effect
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
