ASYMMETRIC INDUCTION IN THE DIELS-ALDER REACTION CATALYZED BY CHIRAL METALLOCENE TRIFLATE COMPLEXES - DRAMATIC EFFECT OF SOLVENT POLARITY

被引：61

作者：

JAQUITH, JB ^{[1
]}

GUAN, JY ^{[1
]}

WANG, ST ^{[1
]}

COLLINS, S ^{[1
]}

机构：

[1] UNIV WATERLOO,DEPT CHEM,WATERLOO,ON N2L 3G1,CANADA

来源：

ORGANOMETALLICS | 1995年 / 14卷 / 03期

关键词：

D O I：

10.1021/om00003a001

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The Diels-Alder cycloaddition reaction between oxazolidinone-based dienophiles 4-6 and cyclopentadiene is efficiently catalyzed by the chiral metallocene complex [(S)-1,2-ethylenebis(eta(5)-tetrahydroindenyl)]Zr(OTf)(2) (2) as well as its titanium analog (3). The level of asymmetric induction. is dramatically affected by solvent polarity; in CH2Cl2 solvent the cycloaddition process is essentially nonstereoselective, whereas in CH3NO2 or 2-nitropropane, higher enantioselectivity (>70% ee) is observed. This behavior can be partially explained with reference to the results of variable-temperature NMR studies of the complexes derived from rac-2 and dienophile 4.

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页码：1079 / 1081

页数：3

相关论文

共 20 条

[1] ET2ALCL COMPLEXES OF AN N-ACYLOXAZOLIDINONE - NMR INVESTIGATION [J].

CASTELLINO, S ;

DWIGHT, WJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (07) :2986-2987

[2] ADDITIONS OF CHIRAL ALLYLTITANOCENES TO ALDEHYDES - DIASTEREOSELECTIVE SYNTHESIS OF HOMOALLYLIC ALCOHOLS WITH A RECYCLABLE CHIRAL TRANSITION-METAL REAGENT [J].

COLLINS, S ;

KUNTZ, BA ;

HONG, Y .

JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (17) :4154-4158

[3] PREPARATION, REACTIVITY, AND X-RAY STRUCTURE OF A CATIONIC ALKOXYZIRCONOCENE COMPLEX [J].

COLLINS, S ;

KOENE, BE ;

RAMACHANDRAN, R ;

TAYLOR, NJ .

ORGANOMETALLICS, 1991, 10 (07) :2092-2094

[4] DESIGNED CATALYST FOR ENANTIOSELECTIVE DIELS-ALDER ADDITION FROM A C2-SYMMETRICAL CHIRAL BIS(OXAZOLINE)-FE(III) COMPLEX [J].

COREY, EJ ;

IMAI, N ;

ZHANG, HY .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (02) :728-729

[5] ASYMMETRIC DIELS-ALDER CYCLO-ADDITION REACTIONS WITH CHIRAL ALPHA, BETA-UNSATURATED N-ACYLOXAZOLIDINONES [J].

EVANS, DA ;

CHAPMAN, KT ;

BISAHA, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (04) :1238-1256

[6] BIS(OXAZOLINE)COPPER(II) COMPLEXES AS CHIRAL CATALYSTS FOR THE ENANTIOSELECTIVE DIELS-ALDER REACTION [J].

EVANS, DA ;

MILLER, SJ ;

LECTKA, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (14) :6460-6461

[7] ENANTIOSELECTIVE, ZIRCONIUM-MEDIATED SYNTHESIS OF ALLYLIC AMINES [J].

GROSSMAN, RB ;

DAVIS, WM ;

BUCHWALD, SL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (06) :2321-2322

[8]

GUAN J, UNPUB

[9] HOMOGENEOUS CATALYSIS - [TICP2(CF3SO3)2] AND [ZRCP2(CF3SO3)2THF], FAST AND EFFICIENT CATALYSTS FOR THE MUKAIYAMA CROSS-ALDOL REACTION [J].

HOLLIS, TK ;

ROBINSON, NP ;

BOSNICH, B .

TETRAHEDRON LETTERS, 1992, 33 (43) :6423-6426

[10]

HOLLIS TK, 1993, TETRAHEDRON, V49, P5415