Cleavage of water-insoluble alkylallylcarbonates catalysed by a palladium/TPPTS/cyclodextrin system: effect of phosphine/cyclodextrin interactions on the reaction rate

被引：31

作者：

Binkowski, U ^{[1
]}

Cabou, J ^{[1
]}

Bricout, H ^{[1
]}

Hapiot, F ^{[1
]}

Monflier, E ^{[1
]}

机构：

[1] Univ Artois, Fac Sci Jean Perrin, F-62307 Lens, France

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2004年 / 215卷 / 1-2期

关键词：

palladium; water-soluble phosphines; cyclodextrins; H-1 and P-31{H-1} NMR; molecular recognition; carbonate cleavage;

D O I：

10.1016/j.molcata.2003.01.001

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

An astonishing aspect of the aqueous organometallic catalysis assisted by randomly methylated p-cyclodextrin (RAME-beta-CD) has been elucidated. Actually, it has been shown that the molecular recognition ability of RAME-beta-CD towards the TPPTS ligand was responsible for a decrease in the rate of a palladium catalysed cleavage reaction of the water-insoluble allylundecylcarbonate. Indeed, when the TPPTS/RAME-beta-CD ratio is too high, the cyclodextrin is poisoned by the ligand and the substrate transfer is diminished. Thus, the use of RAME-beta-CD as an inverse phase transfer catalyst in palladium/TPPTS catalytic system has to be accurately controlled. On the contrary, randomly methylated alpha-cyclodextrin (RAME-alpha-CD) which is not able to associate to TPPTS led to better performances since no decrease in the activity was observed with this cyclodextrin. NMR experiments have been performed throughout this study to substantiate the catalytic results. (C) 2004 Elsevier B.V. All rights reserved.

引用

页码：23 / 32

页数：10

共 50 条

[1] NEW SYNTHETIC APPLICATIONS OF WATER-SOLUBLE ACETATE PD/TPPTS CATALYST GENERATED IN-SITU - EVIDENCE FOR A TRUE PD(0) SPECIES INTERMEDIATE
AMATORE, C
BLART, E
GENET, JP
JUTAND, A
LEMAIREAUDOIRE, S
SAVIGNAC, M
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (21) : 6829 - 6839
[2] Metal-capped α-cyclodextrins:: the crowning of the oligosaccharide torus with precious metals
Armspach, D
Matt, D
[J]. CHEMICAL COMMUNICATIONS, 1999, (12) : 1073 - 1074
[3] Effect of cyclodextrins on the rhodium-catalysed hydrogenation of unsaturated carboxylic acids in water
Arzoumanian, H
Nuel, D
[J]. COMPTES RENDUS DE L ACADEMIE DES SCIENCES SERIE II FASCICULE C-CHIMIE, 1999, 2 (5-6): : 289 - 293
[4] Water-soluble calix[n]arenes as receptor molecules for non-polar substrates and inverse phase transfer catalysts
Baur, M
Frank, M
Schatz, J
Schildbach, F
[J]. TETRAHEDRON, 2001, 57 (32) : 6985 - 6991
[5] Selectivity in sulfonation of triphenyl phosphine
Bhanage, BM
Divekar, SS
Deshpande, RM
Chaudhari, RV
[J]. ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2000, 4 (05) : 342 - 345
[6] Caron L, 2003, EUR J INORG CHEM, P595
[7] Study of the inclusion complexes of β-cyclodextrin with the sodium salt of trisulfonated triphenylphosphine
Caron, L
Tilloy, S
Monflier, E
Wieruszeski, JM
Lippens, G
Landy, D
Fourmentin, S
Surpateanu, G
[J]. JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY, 2000, 38 (1-4) : 361 - 379
[8] Dessoudeix M, 2001, EUR J INORG CHEM, P1797
[9] Gartner R., 1982, [No title captured], Patent No. [DE 32 35 030 Al, 3235030]
[10] Genet J.-P., 1999, IUPAC MONOGRAPHS CHE, P55

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