A tentative kinetic model for chiral amplification in autocatalytic alkylzinc additions

被引：59

作者：

Buhse, T ^{[1
]}

机构：

[1] Univ Autonoma Estado Morelos, Ctr Invest Quim, Cuernavaca 62210, Morelos, Mexico

来源：

TETRAHEDRON-ASYMMETRY | 2003年 / 14卷 / 08期

关键词：

D O I：

10.1016/S0957-4166(03)00128-9

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A simplified kinetic model is proposed to describe stereoselective autocatalysis in specific alkylzinc additions. The model is based on current experimental knowledge and by the use of exclusively mono- or bimolecular processes attempting a chemically and kinetically realistic description. The underlying dynamics were expressed in terms of a template-directed self-replication in which a zinc alkoxide dimer acts as the active autocatalytic species. The model was shown to reproduce previously obtained kinetic data well, to address to the phenomenon of chiral amplification in a semi-quantitative manner, and to enlighten the cause of the effect of the initial enantiomeric excess on the globally observed kinetics. Amplification of enantiomeric excess occurs by considering a homogeneous and entirely symmetric reaction network. (C) 2003 Elsevier Science Ltd. All rights reserved.

引用

页码：1055 / 1061

页数：7

共 32 条

[21] A chiroselective peptide replicator [J].

Saghatelian, A ;

Yokobayashi, Y ;

Soltani, K ;

Ghadiri, MR .

NATURE, 2001, 409 (6822) :797-801

[22]

Sato I, 2000, ANGEW CHEM INT EDIT, V39, P1510, DOI 10.1002/(SICI)1521-3773(20000417)39:8<1510::AID-ANIE1510>3.0.CO

[23]

2-R

[24] Evidence of asymmetric autocatalysis in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde using chiral pyrimidyl alkanol [J].

Sato, I ;

Omiya, D ;

Tsukiyama, K ;

Ogi, Y ;

Soai, K .

TETRAHEDRON-ASYMMETRY, 2001, 12 (14) :1965-1969

[25] Amplification of a slight enantiomeric imbalance in molecules based on asymmetric autocatalysis: The first correlation between high enantiomeric enrichment in a chiral molecule and circularly polarized light [J].

Shibata, T ;

Yamamoto, J ;

Matsumoto, N ;

Yonekubo, S ;

Osanai, S ;

Soai, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (46) :12157-12158

[26] Asymmetric autocatalytic reaction of 3-quinolylalkanol with amplification of enantiomeric excess [J].

Shibata, T ;

Choji, K ;

Hayase, T ;

Aizu, Y ;

Soai, K .

CHEMICAL COMMUNICATIONS, 1996, (10) :1235-1236

[27] Highly enantioselective catalytic asymmetric automultiplication of chiral pyrimidyl alcohol [J].

Shibata, T ;

Morioka, H ;

Hayase, T ;

Choji, K ;

Soai, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (02) :471-472

[28] One-pot asymmetric autocatalytic reaction with remarkable amplification of enantiomeric excess [J].

Shibata, T ;

Hayase, T ;

Yamamoto, J ;

Soai, K .

TETRAHEDRON-ASYMMETRY, 1997, 8 (11) :1717-1719

[29] d- and l-quartz-promoted highly enantioselective synthesis of a chiral organic compound [J].

Soai, K ;

Osanai, S ;

Kadowaki, K ;

Yonekubo, S ;

Shibata, T ;

Sato, I .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (48) :11235-11236

[30] Enantioselective automultiplication of chiral molecules by asymmetric autocatalysis [J].

Soai, K ;

Shibata, T ;

Sato, I .

ACCOUNTS OF CHEMICAL RESEARCH, 2000, 33 (06) :382-390

← 1 2 3 4 →