Highly Diastereoselective Arylations of Substituted Piperidines

被引：120

作者：

Seel, Stephanie ^{[1
]}

Thaler, Tobias ^{[1
]}

Takatsu, Keishi ^{[3
]}

Zhang, Cong ^{[1
]}

Zipse, Hendrik ^{[1
]}

Straub, Bernd F. ^{[2
]}

Mayer, Peter ^{[1
]}

Knochert, Paul ^{[1
]}

机构：

[1] Univ Munich, Dept Chem, D-81377 Munich, Germany

[2] Heidelberg Univ, Inst Organ Chem, D-69120 Heidelberg, Germany

[3] Kyoto Univ, Grad Sch Sci, Dept Chem, Kyoto 6068502, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 13期

基金：

欧洲研究理事会;

关键词：

LITHIOAMINE SYNTHETIC EQUIVALENTS; CATALYZED ALPHA-ARYLATION; N-BOC-PYRROLIDINE; STEREOSELECTIVE-SYNTHESIS; ENANTIOSELECTIVE SYNTHESIS; ASYMMETRIC-SYNTHESIS; CONJUGATE ADDITIONS; COUPLING PROCESSES; PALLADIUM; DERIVATIVES;

D O I：

10.1021/ja201008e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A highly diastereoselective methodology for the preparation of various substituted piperidines via Negishi cross-couplings with (hetero)aryl iodides was developed. Depending on the position of the C-Zn bond relative to the nitrogen (position 2 vs position 4), the stereoselectivity of the coupling can be directed toward either the trans- or cis-2,4-disubstituted products. Density functional theory calculations on the relative stabilities of the Zn and Pd intermediates were performed to explain the high diastereoselectivities obtained. A novel 1,2-migration of Pd further expands this method to the stereoselective preparation of 5-aryl-2,5-disubstituted piperidines.

引用

收藏

页码：4774 / 4777

页数：4

相关论文

共 56 条

[1] Synthesis of enantiopure trans-3,4-disubstituted piperidines.: An enantiodivergent synthesis of (+)- and (-)-paroxetine [J].

Amat, M ;

Bosch, J ;

Hidalgo, J ;

Cantó, M ;

Pérez, M ;

Llor, N ;

Molins, E ;

Miravitlles, C ;

Orozco, M ;

Luque, J .

JOURNAL OF ORGANIC CHEMISTRY, 2000, 65 (10) :3074-3084

[2] An enantioselective synthetic route to cis-2,4-disubstituted and 2,4-bridged piperidines [J].

Amat, Mercedes ;

Perez, Maria ;

Minaglia, Annamaria T. ;

Bosch, Joan .

JOURNAL OF ORGANIC CHEMISTRY, 2008, 73 (17) :6920-6923

[3] Dynamic kinetic resolution and desymmetrization processes:: A straightforward methodology for the enantioselective synthesis of piperidines [J].

Amat, Mercedes ;

Bassas, Oriol ;

Llor, Nuria ;

Canto, Margalida ;

Perez, Maria ;

Molins, Elies ;

Bosch, Joan .

CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (30) :7872-7881

[4] The Regio- and Stereoselective Synthesis of trans-2,3-Dihydropyridine N-oxides and Piperidines [J].

Andersson, Hans ;

Gustafsson, Magnits ;

Bostrom, Dan ;

Olsson, Roger ;

Almqvist, Fredrik .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (18) :3288-3291

[5] Asymmetric routes to substituted piperidines [J].

Bailey, PD ;

Millwood, PA ;

Smith, PD .

CHEMICAL COMMUNICATIONS, 1998, (06) :633-640

[6] Silver Ion-induced Grob Fragmentation of γ-Amino Iodides: Highly Stereoselective Synthesis of Polysubstituted Piperidines [J].

Barbe, Guillaume ;

St-Onge, Miguel ;

Charette, Andre B. .

ORGANIC LETTERS, 2008, 10 (23) :5497-5499

[7] ALPHA-LITHIOAMINE SYNTHETIC EQUIVALENTS - SYNTHESES OF DIASTEREOISOMERS FROM BOC DERIVATIVES OF CYCLIC AMINES [J].

BEAK, P ;

LEE, WK .

JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (05) :1109-1117

[8] ALPHA-LITHIOAMINE SYNTHETIC EQUIVALENTS - SYNTHESES OF DIASTEREOISOMERS FROM THE BOC PIPERIDINES [J].

BEAK, P ;

LEE, WK .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (09) :2578-2580

[9] Application of Catalytic Dynamic Resolution of N-Boc-2-lithiopiperidine to the Asymmetric Synthesis of 2-Aryl and 2-Vinyl Piperidines [J].

Beng, Timothy K. ;

Gawley, Robert E. .

ORGANIC LETTERS, 2011, 13 (03) :394-397

[10] Catalytic Asymmetric Synthesis of Piperidines from Pyrrolidine: Concise Synthesis of L-733,060 [J].

Bilke, Julia L. ;

Moore, Stephen P. ;

O'Brien, Peter ;

Gilday, John .

ORGANIC LETTERS, 2009, 11 (09) :1935-1938

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