Calix[4]arene-based Zn2+ complexes as shape- and size-selective catalysts of ester cleavage

被引:27
作者
Cacciapaglia, R
Casnati, A
Mandolini, L
Reinhoudt, DN
Salvio, R
Sartori, A
Ungaro, R
机构
[1] Univ Roma La Sapienza, Dipartimento Chim, I-00185 Rome, Italy
[2] Univ Roma La Sapienza, CNR, Sez Meccanismi Reaz, IMC, I-00185 Rome, Italy
[3] Univ Parma, Dipartimento Chim Organ & Ind, I-43100 Parma, Italy
[4] Univ Twente, Lab Supramol Chem & Technol, MESA Res Inst, NL-7500 AE Enschede, Netherlands
关键词
D O I
10.1021/jo050196r
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The kinetics of methanolysis of a number of esters endowed with a carboxylate anchoring group have been investigated in the presence of di- and trinuclear Zn2+ complexes of calix[4]arenes functionalized at the upper rim with nitrogen ligands. The results (i) emphasize the importance of a good match between ester size and intermetal distance, (ii) reveal a substrate independent superiority of the 1,2-vicinal dinuclear catalyst 1-Zn-2 to its 1,3-distal regioisomer 2-Zn-2, and (iii) provide further evidence for the concurrence of the three metal ions of 3-Zn-3 in the catalytic mechanism.
引用
收藏
页码:5398 / 5402
页数:5
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