Enantioselective synthesis of ansa-zirconocenes

被引：30

作者：

LoCoco, MD ^{[1
]}

Jordan, RF ^{[1
]}

机构：

[1] Univ Chicago, Dept Chem, Chicago, IL 60637 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 43期

关键词：

D O I：

10.1021/ja045245g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction of the chiral chelated bis-amide complex Zr{(2R,4R)-PhNCHMeCH2CHMeNPh}Cl2(THF)2 (R,R-7) with lithium ansa-bis-indenyl reagents Li2[SBI](Et2O) (8a, SBI = (1-indenyl)2SiMe2) or Li2[EBI](Et2O) (8b, EBI = 1,2-(1-indenyl)2ethane) in THF affords the corresponding ansa-zirconocenes S,S-(SBI)Zr{(2R,4R)-PhNCHMeCH2CHMeNPh} (S,S,R,R-9a) or S,S-(EBI)Zr{(2R,4R)-PhNCHMeCH2CHMeNPh} (S,S,R,R-9b) in >95% isolated yield and >99% enantiomeric excess. Compound 9b was converted to the corresponding enantiomerically pure dichloride S,S-(EBI)ZrCl2 (S,S-10b) in 91% isolated yield by reaction with HCl in Et2O. The chiral diamine (2R,4R)-HPhNCHMeCH2CHMeNHPh (R,R-5) was recovered from this reaction. Copyright © 2004 American Chemical Society.

引用

收藏

页码：13918 / 13919

页数：2

相关论文

共 34 条

[1] Stereoselective chelate-controlled addition of Grignard reagents to unsaturated medium-ring heterocycles [J].

Adams, JA ;

Heron, NM ;

Koss, AM ;

Hoveyda, AH .

JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (03) :854-860

[2]

[Anonymous], ANGEW CHEM INT EDIT

[3] Epoxide-opening and group-transfer reactions mediated by monomeric zirconium imido complexes [J].

Blum, SA ;

Walsh, PJ ;

Bergman, RG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (47) :14276-14277

[4] Asymmetric catalysis of the Diels-Alder reaction using dicationic zirconocene complexes [J].

Bondar, GV ;

Aldea, R ;

Levy, CJ ;

Jaquith, JB ;

Collins, S .

ORGANOMETALLICS, 2000, 19 (06) :947-949

[5] STEREOSPECIFIC OLEFIN POLYMERIZATION WITH CHIRAL METALLOCENE CATALYSTS [J].

BRINTZINGER, HH ;

FISCHER, D ;

MULHAUPT, R ;

RIEGER, B ;

WAYMOUTH, RM .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1995, 34 (11) :1143-1170

[6] ORGANOBORANES FOR SYNTHESIS .8. REACTION OF ORGANOBORANES WITH REPRESENTATIVE ORGANIC AZIDES - A GENERAL STEREOSPECIFIC SYNTHESIS OF SECONDARY-AMINES AND N-SUBSTITUTED AZIRIDINES [J].

BROWN, HC ;

MIDLAND, MM ;

LEVY, AB ;

SUZUKI, A ;

SONO, S ;

ITOH, M .

TETRAHEDRON, 1987, 43 (18) :4079-4088

[7] An improved procedure for the resolution of (rac)-ethylenebis(tetrahydroindenyl)-titanium derivatives [J].

Chin, B ;

Buchwald, SL .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (16) :5650-5651

[8] Improved procedure for the preparation of enantiomerically pure ethylenebis(tetrahydroindenyl)zirconium derivatives [J].

Chin, B ;

Buchwald, SL .

JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (07) :2267-2268

[9] Stereoselective propene insertion reactions of rac-(EBI)Zr(eta(2)-pyridyl)(+) complexes [J].

Dagorne, S ;

Rodewald, S ;

Jordan, RF .

ORGANOMETALLICS, 1997, 16 (25) :5541-5555

[10] SYNTHESIS, STRUCTURE, AND PROPERTIES OF CHIRAL TITANIUM AND ZIRCONIUM COMPLEXES BEARING BIARYL STRAPPED SUBSTITUTED CYCLOPENTADIENYL LIGANDS [J].

ELLIS, WW ;

HOLLIS, TK ;

ODENKIRK, W ;

WHELAN, J ;

OSTRANDER, R ;

RHEINGOLD, AL ;

BOSNICH, B .

ORGANOMETALLICS, 1993, 12 (11) :4391-4401

← 1 2 3 4 →