NCN子复合物:它们通过连接物引入路径的制备及其催化性质
Kazuhiro Takenaka1, Maki Minakawa, Yasuhiro Uozumi
1Institute for Molecular Science (IMS), The Graduate University for Advanced Studies, and CREST, Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan.
Journal of the American Chemical Society
|September 1, 2005
概括
新的NCN刀拉复合体是使用一种新的连接物引入路径来合成的. 这些复合物在关键有机反应中表现出高的催化活性和酶选择性,展示了它们在催化中的潜力.
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.
- 有机合成 有机合成
背景情况:
- 复合物是有机合成中的关键催化剂.
- NCN子连接物为稳定金属中心提供独特的协调特性.
- 为推进催化应用,开发高效的合成路径到新型复合物是必不可少的.
研究的目的:
- 为了合成一系列多样化的NCN子合物复合物.
- 为了研究一种新的连接物引入路径来制备它们.
- 评估这些复合体在赫克和不对称迈克尔反应中的催化性能.
主要方法:
- 通过脱水连接物引入,合成NCN刀拉复合体.
- 使用proline anilides制备奇拉NCN具复合物.
- 使用NMR光谱学进行表征.
- 在赫克和不对称迈克尔反应中的催化评价.
主要成果:
- 成功合成各种NCN子复合物,产量优异 (71-98%).
- 核磁共振研究证实了中间体和最终复合体之间的平衡.
- 在高产量中制备了基拉尔NCN罗胺醇拉复合物.
- 在赫克和不对称的迈克尔反应中表现出高的催化活性和酶选择性.
结论:
- 开发的连接物引入路径对于合成NCN子拉复合体是有效的.
- 合成的复合物,无论是achiral和chiral,都是非常有效的催化剂.
- 这些NCN子复合物显示出对不对称催化剂应用的重大前景.
相关概念视频
Coordination Compounds and Nomenclature
In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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...
Valence Bond Theory
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Ziegler–Natta Chain-Growth Polymerization: Overview
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta catalyst, high molecular...
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...


