Dinuclear barium(II) complexes based on a calix[4]arene scaffold as catalysts of acyl transfer

被引:21
作者
Cacciapaglia, R
Casnati, A
Di Stefano, S
Mandolini, L
Paolemili, D
Reinhoudt, DN
Sartori, A
Ungaro, R
机构
[1] CNR, Sez Meccan Reaz, IMC, I-00185 Rome, Italy
[2] Univ Roma La Sapienza, Dipartimento Chim, I-00185 Rome, Italy
[3] Univ Parma, Dipartimento Chim Organ & Ind, I-43100 Parma, Italy
[4] Univ Twente, Fac Chem Technol, Labs Supramol Chem & Technol, NL-7500 AE Enschede, Netherlands
[5] MESA, Res Inst, NL-7500 AE Enschede, Netherlands
关键词
calixarenes; crown compounds; effective molarity; metallocatalysts; supramolecular chemistry;
D O I
10.1002/chem.200400294
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Two novel regioisomeric calix[4]arene derivatives (2 and 3), decorated with two aza[18]crown-6 units at vicinal (1,2) or diagonal (1,3) positions of the upper rim, were synthesized. The catalytic activities of their dinuclear Ba2+ complexes were investigated in the ethanolysis of esters 8-11, endowed with a carboxylate anchoring group. Major results are as follows: 1) the two metal ions in the dinuclear catalysts work together in a cooperative fashion; 2) the vicinal calix[4]arene catalyst 2 is far superior to its diagonal regioisomer 3 in the reactions of all of the investigated esters; and 3) the distance between the carboxylate and ester carbonyl, which increases regularly from 8 to 11, influences reactivity of catalytic ester cleavage in a way that is decidedly suggestive of the importance of a good match between ester size and metal-to-metal distance. However, the superiority of the vicinal catalyst 2 relative to 3 cannot be explained on the basis of the putative match of ester size to intermetal distance, thus providing an indication that additional, still poorly understood effects may contribute significantly to catalytic efficiency.
引用
收藏
页码:4436 / 4442
页数:7
相关论文
共 19 条
[1]  
Cacciapaglia R, 1999, ANGEW CHEM INT EDIT, V38, P348, DOI 10.1002/(SICI)1521-3773(19990201)38:3<348::AID-ANIE348>3.0.CO
[2]  
2-D
[3]   Effective molarities in supramolecular catalysis of two-substrate reactions [J].
Cacciapaglia, R ;
Di Stefano, S ;
Mandolini, L .
ACCOUNTS OF CHEMICAL RESEARCH, 2004, 37 (02) :113-122
[4]   The bis-barium complex of a butterfly crown ether as a phototunable supramolecular catalyst [J].
Cacciapaglia, R ;
Di Stefano, S ;
Mandolini, L .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (08) :2224-2227
[5]   Size-selective catalysis of ester and anilide cleavage by the dinuclear barium(II) complexes of cis- and trans-stilbenobis(18-crown-6) [J].
Cacciapaglia, R ;
Di Stefano, S ;
Mandolini, L .
JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (02) :521-525
[6]  
Cacciapaglia R, 2000, CALIXARENES IN ACTION, P241, DOI 10.1142/9781848160354_0010
[7]   A dinuclear strontium(II) complex as substrate-selective catalyst of ester cleavage [J].
Cacciapaglia, R ;
Di Stefano, S ;
Mandolini, L .
JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (17) :5926-5928
[8]  
CACCIAPAGLIA R, 1999, ANGEW CHEM, V111, P359
[9]  
Casnati A, 1996, GAZZ CHIM ITAL, V126, P99
[10]   Synthesis and characterization of imidazole-substituted calix[4]arenes as simple enzyme-mimics with acyltransferase activity [J].
Dospil, G ;
Schatz, J .
TETRAHEDRON LETTERS, 2001, 42 (44) :7837-7840