A Highly Enantioselective Zirconium Catalyst for Intramolecular Alkene Hydroamination: Significant Isotope Effects on Rate and Stereoselectivity

被引：109

作者：

Manna, Kuntal ^{[1
,2
]}

Xu, Songchen ^{[1
,2
]}

Sadow, Aaron D. ^{[1
,2
]}

机构：

[1] Iowa State Univ, Dept Chem, 1605 Gilman Hall, Ames, IA 50011 USA

[2] Iowa State Univ, Ames Lab, Ames, IA USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2011年 / 50卷 / 08期

基金：

美国国家科学基金会;

关键词：

enantioselectivity; hydroamination; isotope effects; oxazolines; pyrrolidines; ASYMMETRIC HYDROAMINATION; METAL-CATALYSTS; COMPLEXES; MECHANISM; AMINOALKENE; CYCLIZATION; OLEFINS; ALKYNES;

D O I：

10.1002/anie.201006163

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Zirconium catalysts sparkle: A new chiral zirconium complex has been used to catalyze hydroamination reactions to cyclize aminopentenes into 2-methylpyrrolidines (see scheme). The rate law supports a mechanism involving a reversible substrate-catalyst interaction that precedes the rate-determining step. A new mechanism for zirconium-catalyzed hydroamination has been proposed based on kinetic isotope effects and the significant effect of isotopic substitution on enantioselectivity. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：1865 / 1868

页数：4

共 28 条

[1] Intramolecular hydroamination of unactived olefins with Ti(NMe2)4 as a precatalyst [J].

Bexrud, JA ;

Beard, JD ;

Leitch, DC ;

Schafer, LL .

ORGANIC LETTERS, 2005, 7 (10) :1959-1962

[2]

Cornish-Bowden A., 2004, FUNDAMENTALS ENZYME, V3rd, P137

[3] Bis(oxazolinyl)phenylborane: A Lewis acid-containing ligand for methide abstraction-based coordination to aluminum(III) [J].

Dunne, James F. ;

Manna, Kuntal ;

Wiench, Jerzy W. ;

Ellern, Arkady ;

Pruski, Marek ;

Sadow, Aaron D. .

DALTON TRANSACTIONS, 2010, 39 (02) :641-653

[4] Concerted C-N and C-H Bond Formation in a Magnesium-Catalyzed Hydroamination [J].

Dunne, James F. ;

Fulton, D. Bruce ;

Ellern, Arkady ;

Sadow, Aaron D. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (50) :17680-17683

[5] STEREOSELECTION EFFECTS IN THE CATALYTIC HYDROAMINATION CYCLIZATION OF AMINOOLEFINS AT CHIRAL ORGANOLANTHANIDE CENTERS [J].

GAGNE, MR ;

BRARD, L ;

CONTICELLO, VP ;

GIARDELLO, MA ;

STERN, CL ;

MARKS, TJ .

ORGANOMETALLICS, 1992, 11 (06) :2003-2005

[6] ORGANOLANTHANIDE-CATALYZED HYDROAMINATION - A KINETIC, MECHANISTIC, AND DIASTEREOSELECTIVITY STUDY OF THE CYCLIZATION OF N-UNPROTECTED AMINO OLEFINS [J].

GAGNE, MR ;

STERN, CL ;

MARKS, TJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (01) :275-294

[7] CHIRAL ORGANOLANTHANIDES DESIGNED FOR ASYMMETRIC CATALYSIS - A KINETIC AND MECHANISTIC STUDY OF ENANTIOSELECTIVE OLEFIN HYDROAMINATION/CYCLIZATION AND HYDROGENATION BY C-1-SYMMETRICAL ME(2)SI(ME(4)C(5))(C(5)H(3)R-ASTERISK)LN COMPLEXES WHERE R-ASTERISK=CHIRAL AUXILIARY [J].

GIARDELLO, MA ;

CONTICELLO, VP ;

BRARD, L ;

GAGNE, MR ;

MARKS, TJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (22) :10241-10254

[8] Catalytic alkene cyclohydroamination via an imido mechanism [J].

Gott, Andrew L. ;

Clarke, Adam J. ;

Clarkson, Guy J. ;

Scott, Peter .

CHEMICAL COMMUNICATIONS, 2008, (12) :1422-1424

[9]

Gribkov D. V., 2004, ANGEW CHEM, V116, P5659

[10] 3,3′-bis(trisarylsilyl)-substituted binaphtholate rare earth metal catalysts for asymmetric hydroamination [J].

Gribkov, DV ;

Hultzsch, KC ;

Hampel, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (11) :3748-3759

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