Consequences of Cooperativity in Racemizing Supramolecular Systems

被引：38

作者：

Cantekin, Seda ^{[1
]}

ten Eikelder, Huub M. M. ^{[2
]}

Markvoort, Albert J. ^{[2
]}

Veld, Martijn A. J. ^{[1
]}

Korevaar, Peter A. ^{[1
]}

Green, Mark M. ^{[3
]}

Palmans, Anja R. A. ^{[1
]}

Meijer, E. W. ^{[1
]}

机构：

[1] Eindhoven Univ Technol, Inst Complex Mol Syst, Lab Macromol & Organ Chem, NL-5600 MB Eindhoven, Netherlands

[2] Eindhoven Univ Technol, Inst Complex Mol Syst, Biomodeling & Bioinformat Grp, NL-5600 MB Eindhoven, Netherlands

[3] NYU, Dept Chem & Biol Sci, Polytech Inst, Brooklyn, NY 11201 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2012年 / 51卷 / 26期

基金：

美国国家科学基金会;

关键词：

deracemization; enantiomeric excess; nonlinear effects; self-assembly; supramolecular chemistry; MAJORITY-RULES PRINCIPLE; ASYMMETRIC CATALYSIS; DILUTE-SOLUTION; SOLID-STATE; DERACEMIZATION; AMPLIFICATION; EMERGENCE; CHIRALITY;

D O I：

10.1002/anie.201201701

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Saluting the sergeant: Phg-BTA (see scheme) cooperatively self-assembles into helical aggregates and shows unprecedented racemization behavior in the presence of base. In thermodynamically controlled conditions, the addition of a small amount of chiral auxiliary to this mixture results in a deracemization reaction and a final enantiomeric excess of 32 %. A theoretical model is presented to understand in detail the results obtained. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：6426 / 6431

页数：6

共 30 条

[1] Spontaneous Deracemization [J].

Amabilino, David B. ;

Kellogg, Richard M. .

ISRAEL JOURNAL OF CHEMISTRY, 2011, 51 (10) :1034-1040

[2]

[Anonymous], 2007, ANGEW CHEM

[3] Chiral amplification in columns of self-assembled N,N′,N"-tris((S)-3,7-dimethyloctyl)benzene-1,3,5-tricarboxamide in dilute solution [J].

Brunsveld, L ;

Schenning, APHJ ;

Broeren, MAC ;

Janssen, HM ;

Vekemans, JAJM ;

Meijer, EW .

CHEMISTRY LETTERS, 2000, (03) :292-293

[4]

ELIEL EL, 1994, STEREOCHEMISTRY ORGA, P426

[5]

Faber K, 2001, CHEM-EUR J, V7, P5004, DOI 10.1002/1521-3765(20011203)7:23<5004::AID-CHEM5004>3.0.CO

[6]

2-X

[7] NONLINEAR EFFECTS IN ASYMMETRIC CATALYSIS [J].

GUILLANEUX, D ;

ZHAO, SH ;

SAMUEL, O ;

RAINFORD, D ;

KAGAN, HB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (21) :9430-9439

[8] The nature of the thermodynamically controlled deracemization of 2-benzylcyclohexanone using (R,R)-(-)-trans-2,3-bis(hydroxydiphenylmethyl)-1,4-dioxaspiro[5.4]decane:: a crystallographic result of inclusion complex [J].

Kaku, H ;

Takaoka, S ;

Tsunoda, T .

TETRAHEDRON, 2002, 58 (17) :3401-3407

[9] Theoretical models of nonlinear effects in two-component cooperative supramolecular copolymerizations [J].

Markvoort, Albert J. ;

ten Eikelder, Huub M. M. ;

Hilbers, Peter A. J. ;

de Greef, Tom F. A. ;

Meijer, E. W. .

NATURE COMMUNICATIONS, 2011, 2

[10]

Mislow K., 1965, INTRO STEREOCHEMISTR, P69

← 1 2 3 →