Di- and trinuclear Zn2+ complexes of calix[4]arene based ligands as catalysts of acyl and phosphoryl transfer reactions

被引:47
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, IMC, CNR, Sez Meccan Reaz, I-00185 Rome, Italy
[3] Univ Parma, Dipartimento Chim Organ & Ind, I-43100 Parma, Italy
[4] Univ Twente, MESA Res Inst, Lab Supramol Chem & Technol, NL-7500 AE Enschede, Netherlands
关键词
D O I
10.1021/jo0487350
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst-substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal much greater than 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism.
引用
收藏
页码:624 / 630
页数:7
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