A base-free copper-assisted synthesis of <i>C</i><sub>2</sub>-symmetric spirotelluranes and biaryls based on divergent stoichiometry of Na<sub>2</sub>Te
methodology has been developed for the preparation of biologically important C2-symmetric spirodiaza, benzyloxy and benzoxytelluranes from 2-bromo-N-aryl benzamides, benzyl alcohols, and benzoic acids by using the tellurium dianion (Te2−) under base-free conditions. Furthermore, C–C coupled biaryl 1,1′-diamides have been prepared by using an excess of Na2Te under the same reaction conditions. The synthesized
已经开发了一种一锅法 Cu( I ) 辅助合成方法,用于通过使用碲双阴离子从 2-溴-N-芳基苯甲酰胺、苯甲醇和苯甲酸制备具有生物学重要意义的C 2 -对称螺二氮杂、苯甲氧基和苯甲氧基碲烷。 (Te 2- ) 在无碱条件下。此外,在相同的反应条件下,通过使用过量的 Na 2 Te 制备了 C-C 偶联联芳基 1,1'-二酰胺。合成的螺二氮杂碲烷可作为还原 H 2 O 2和硝基-迈克尔反应的有效催化剂。
Bottom-Up Assembly of a Highly Efficient Metal–Organic Framework for Cooperative Catalysis
In this study, we demonstrate a bottom-up assembly of a monomeric copper complex and a two-dimensional (2-D) heterometallic metal-organic framework (MOF) from a carboxylate-functionalized tridentate Schiff base ligand and metal ions. The obtained 2-D MOF features a unique bimetallic copper center which is different from its monometallic precursor and acts as an efficient heterogeneous catalyst for the Friedel-Crafts reaction and Henry reaction. The MOF catalyst shows a remarkably superior activity compared to its homogeneous counterparts in a wide range of substrates. It is presumably ascribed to the dual activation of the substrates by the active bimetallic copper center confined in the MOF network, which is supported by the significant changes in catalytic activity at low catalyst/substrates ratios when using the 2-D MOF and its precursor as catalysts, respectively. Moreover, the MOF catalyst also shows an excellent stability and recyclability. Our work, therefore, provides a stepwise strategy to design a heterogeneous cooperative catalyst, by taking advantage of the modulated structure of MOF and tunable functionality of the tridentate Schiff base, with high performance in a variety of organic synthesis.
A combination of water and microwave irradiation promotes the catalyst-free addition of pyrroles and indoles to nitroalkenes
作者:Margherita De Rosa、Annunziata Soriente
DOI:10.1016/j.tet.2010.02.055
日期:2010.4
A combination of water and microwave irradiation was used for the first time to perform a catalyst-free nitro-Michael addition of pyrroles and indoles. Under superheated conditions, the water trends to ionize by changing its chemical and physical properties. Therefore, we performed a new green-protocol using the water either as environmentally no harm solvent or as catalyst. The reaction success is independent from the kind of pyrrole, indole or nitroalkenes rapidly affording the corresponding adducts and giving excellent yields. (C) 2010 Elsevier Ltd. All rights reserved.