Enantioselective hydrolysis of long chain α-amino acid esters by chiral sulfur-containing macrocyclic metallomicelles

被引：20

作者：

You, JS ^{[1
]}

Yu, XQ ^{[1
]}

Li, XS ^{[1
]}

Yan, QS ^{[1
]}

Xie, RG ^{[1
]}

机构：

[1] Sichuan Univ, Dept Chem, Chengdu 610064, Peoples R China

来源：

TETRAHEDRON-ASYMMETRY | 1998年 / 9卷 / 07期

基金：

中国国家自然科学基金;

关键词：

D O I：

10.1016/S0957-4166(98)00098-6

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A novel chiral lipophilic sulfur-containing macrocyclic ligand 5 with bis-pendant alcohols in the proximity of the coordination center has been synthesized. Its metal ion complexes have been investigated as catalysts for the enantioselective hydrolysis of long chain alpha-amino acid esters in aqueous comicellar solution with Brij35. Large rate accelerations (up to 220 times) and moderate enantioselectivities (up to 4.85 (k(S)/k(R))) employing the macrocyclic 5-Cu2+ have been observed, whereas the acyclic 3-Cu2+ exhibits less reactivity and stereoselectivity. Taking the analogous ligand 4, lacking the hydroxy groups leads to a dramatic rate decrease, and an inversion of enantioselectivity is observed. The pKa value of the hydroxyl bound to Cu2+ is, determined to be pKa=7.2 under our micellar reaction conditions. (C) 1998 Elsevier Science Ltd. All rights reserved.

引用

页码：1197 / 1203

页数：7

共 22 条

[1] A METHOD OF SYNTHESIS OF LONG PEPTIDE CHAINS USING A SYNTHESIS OF OXYTOCIN AS AN EXAMPLE
BODANSZKY, M
DUVIGNEAUD, V
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1959, 81 (21) : 5688 - 5691
[2] MICELLAR CATALYSIS OF ORGANIC-REACTIONS .33. AMIDE HYDROLYSIS IN NEUTRAL SOLUTION IN THE PRESENCE OF A COPPER-CONTAINING MICELLE
BROXTON, TJ
COX, RA
[J]. CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1993, 71 (05): : 670 - 673
[3] Source of catalysis of dephosphorylation of p-nitrophenyldiphenylphosphate by metallomicelles
Bunton, CA
Scrimin, P
Tecilla, P
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1996, (03): : 419 - 425
[4] Chiral lipophilic ligands .5. Enantioselective ester cleavage of alpha-amino esters by Cu(II) complexes of chiral diamino alcohols in aqueous surfactants solutions
Cleij, MC
Mancin, F
Scrimin, P
Tecilla, P
Tonellato, U
[J]. TETRAHEDRON, 1997, 53 (01) : 357 - 368
[5] Chiral lipophilic ligands .3. Control of enantioselectivity in copper(II)-catalyzed cleavage of alpha-amino acid esters by aggregate morphology
Cleij, MC
Scrimin, P
Tecilla, P
Tonellato, U
[J]. LANGMUIR, 1996, 12 (12) : 2956 - 2960
[6] ZN(++)-COMPLEXES AS MODELS OF METALLOENZYMES IN MICELLAR ESTEROLYSIS - LIGAND STRUCTURE-DEPENDENT STOICHIOMETRY OF THE COMPLEXES
FAIVRE, V
BREMBILLA, A
ROIZARD, D
LOCHON, P
[J]. TETRAHEDRON LETTERS, 1991, 32 (02) : 193 - 196
[7] FUNCTIONAL MICELLAR CATALYSIS .8. CATALYSIS OF THE HYDROLYSIS OF PARA-NITROPHENYL PICOLINATE BY METAL-CHELATING MICELLES CONTAINING COPPER(II) OR ZINC(II)
FORNASIER, R
MILANI, D
SCRIMIN, P
TONELLATO, U
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1986, (02): : 233 - 237
[8] SPECIFICITY AND STEREOSPECIFICITY OF ALPHA-CHYMOTRYPSIN
INGLES, DW
KNOWLES, JR
[J]. BIOCHEMICAL JOURNAL, 1967, 104 (02) : 369 - &
[9] Hydrolysis of lipophilic esters catalyzed by a Zinc(II) complex of a long alkyl-pendant macrocyclic tetraamine in Micellar solution
Kimura, E
Hashimoto, H
Koike, T
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (45) : 10963 - 10970
[10] Enantioselective reduction of aromatic ketones with borane catalyzed by (R)-4-thiazolidinecarboxylic acids or (R)-4-thiazolidine methanol
Li, XS
Xie, RG
[J]. TETRAHEDRON-ASYMMETRY, 1996, 7 (10) : 2779 - 2782

← 1 2 3 →