Dynamic thermodynamic resolution: Control of enantioselectivity through diastereomeric equilibration

被引：174

作者：

Beak, P ^{[1
]}

Anderson, DR ^{[1
]}

Curtis, MD ^{[1
]}

Laumer, JM ^{[1
]}

Pippel, DJ ^{[1
]}

Weisenburger, GA ^{[1
]}

机构：

[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA

来源：

ACCOUNTS OF CHEMICAL RESEARCH | 2000年 / 33卷 / 10期

关键词：

D O I：

10.1021/ar000077s

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A theoretical foundation, tools for recognition:and control, and recent examples of a class of asymmetric transformation termed dynamic thermodynamic resolution are presented. Enantioselective reaction pathways that involve an induced diastereomeric equilibration to intermediates, which are configurationally stable bn the time scale of a subsequent reaction, are illustrated. Dynamic thermodynamic resolution differs from the classic, well-documented pathways of kinetic resolution and dynamic kinetic resolution in that equilibration and resolution can be operative on one system in separate controllable steps. This approach offers a high level of flexibility and provides multiple opportunities for optimization of enantioselectivity.

引用

页码：715 / 727

页数：13

共 34 条

[1] Ahlbrecht H, 1999, SYNTHESIS-STUTTGART, P365
[2] Pathways for stereoinformation transfer: Enhanced enantioselectivity via diastereomeric recycling of organolithium/(-)-sparteine complexes
Basu, A
Gallagher, DJ
Beak, P
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (17) : 5718 - 5719
[3] Control of the enantiochemistry of electrophilic substitutions of N-pivaloyl-alpha-lithio-o-ethylaniline: Stereoinformation transfer based on the method of organolithium formation
Basu, A
Beak, P
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (06) : 1575 - 1576
[4] Regioselective, diastereoselective, and enantioselective lithiation-substitution sequences: Reaction pathways and synthetic applications
Beak, P
Basu, A
Gallagher, DJ
Park, YS
Thayumanavan, S
[J]. ACCOUNTS OF CHEMICAL RESEARCH, 1996, 29 (11) : 552 - 560
[5] Behrens K, 1998, EUR J ORG CHEM, V1998, P2397
[6] Dynamic resolutions in asymmetric synthesis
Caddick, S
Jenkins, K
[J]. CHEMICAL SOCIETY REVIEWS, 1996, 25 (06) : 447 - &
[7] Carlier PR, 1998, ANGEW CHEM INT EDIT, V37, P2252, DOI 10.1002/(SICI)1521-3773(19980904)37:16<2252::AID-ANIE2252>3.0.CO
[8] 2-Z
[9] Clayden J, 1999, ANGEW CHEM INT EDIT, V38, P2556, DOI 10.1002/(SICI)1521-3773(19990903)38:17<2556::AID-ANIE2556>3.0.CO
[10] 2-Q

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