Dendritic styryl TADDOLs as novel polymer cross-linkers: First application in an enantioselective Et2Zn addition mediated by a polymer-incorporated titanate

被引:93
作者
Rheiner, PB [1 ]
Sellner, H [1 ]
Seebach, D [1 ]
机构
[1] ETH ZENTRUM,ORGAN CHEM LAB,CH-8092 ZURICH,SWITZERLAND
关键词
D O I
10.1002/hlca.19970800702
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
TADDOLs (alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-dimethanols) with dendritic branches attached to the aryl groups and with 8 or 16 peripheral styryl double bonds have been synthesized (4 and 5). With these compounds, dendritic molecules were employed for the first time as cross-linkers in a polymerization. The resulting polystyrene was loaded with titanate (Ti(OCHMe2)(4)) to generate polymer beads incorporating Ti-TADDOLate centers (Figs. 1 and 2) for enantioselective catalysis (Et2Zn addition to PhCHO). Compared with conventionally polymer-attached, insoluble Ti-TADDOLates (cf. 3), the new materials have a much higher catalytic activity, rather close to that of soluble analogs (Fig. 3).
引用
收藏
页码:2027 / 2032
页数:6
相关论文
共 17 条
[11]   2,2-DIMETHYL-ALPHA,ALPHA,ALPHA'ALPHA'-TETRAKIS(BETA-NAPHTHYL)-1,3-DIOXOLAN-4,5-DIMETHANOL(DINOL) FOR THE TITANATE-MEDIATED ENANTIOSELECTIVE ADDITION OF DIETHYLZINC TO ALDEHYDES [J].
SCHMIDT, B ;
SEEBACH, D .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1991, 30 (10) :1321-1323
[12]  
Schmidt B., 1991, ANGEW CHEM INT EDIT, V103, P1383
[13]   SYNTHESIS OF CHIRAL STARBURST DENDRIMERS FROM PHB-DERIVED TRIOLS AS CENTRAL CORES [J].
SEEBACH, D ;
LAPIERRE, JM ;
GREIVELDINGER, G ;
SKOBRIDIS, K .
HELVETICA CHIMICA ACTA, 1994, 77 (07) :1673-1688
[14]   ENANTIOSELECTIVE AND DIASTEREOSELECTIVE TITANIUM-TADDOLATE CATALYZED ADDITION OF DIETHYL AND BIS(3-BUTEN-1-YL) ZINC TO ALDEHYDES - A FULL ACCOUNT WITH PREPARATIVE DETAILS [J].
SEEBACH, D ;
BECK, AK ;
SCHMIDT, B ;
WANG, YM .
TETRAHEDRON, 1994, 50 (15) :4363-4384
[15]   ON THE MECHANISMS OF ENANTIOSELECTIVE REACTIONS USING ALPHA,ALPHA,ALPHA',ALPHA'-TETRAARYL-1,3-DIOXOLANE-4,5-DIMETHANOL(TADDOL)-DERIVED TITANATES - DIFFERENCES BETWEEN C2-SYMMETRICAL AND C1-SYMMETRICAL TADDOLS FACTS, IMPLICATIONS AND GENERALIZATIONS [J].
SEEBACH, D ;
PLATTNER, DA ;
BECK, AK ;
WANG, YM ;
HUNZIKER, D ;
PETTER, W .
HELVETICA CHIMICA ACTA, 1992, 75 (07) :2171-2209
[16]   Polymer- and dendrimer-bound Ti-TADDOLates in catalytic (and stoichiometric) enantioselective reactions: Are pentacoordinate cationic Ti complexes the catalytically active species? [J].
Seebach, D ;
Marti, RE ;
Hintermann, T .
HELVETICA CHIMICA ACTA, 1996, 79 (06) :1710-1740
[17]  
Seebach D, 1997, CHIMIA, V51, P293