Partial Kinetic Resolution of Oxanorbornenes by Ring-Opening Metathesis Polymerization with a Chiral Ruthenium Initiator

被引：11

作者：

Daeffler, Christopher S. ^{[1
]}

Miyake, Garret M. ^{[1
]}

Li, Jean ^{[1
]}

Grubbs, Robert H. ^{[1
]}

机构：

[1] CALTECH, Div Chem & Chem Engn, Arnold & Mabel Beckman Lab Chem Synth, Pasadena, CA 91125 USA

来源：

ACS MACRO LETTERS | 2014年 / 3卷 / 01期

关键词：

ENANTIOSELECTIVE SYNTHESIS; CLOSING METATHESIS; ALPHA-OLEFINS; CATALYSTS; POLYMERS;

D O I：

10.1021/mz4005953

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

We report the first kinetic resolution by ring-opening metathesis polymerization (KR-ROMP). The polymerization profile showed a solvent-dependent variation of selectivity (S) over the course of the reaction. In tetrahydrofuran and dichloromethane, the resolution selectivity increased over the course of the reaction, while in toluene the selectivity was much higher in the beginning of the reaction and decreased throughout. Evidence suggests that the change in selectivity might be attributed to the chiral secondary structure of the growing polymer chain.

引用

页码：102 / 104

页数：3

共 32 条

[1] Chemical genetics screen for enhancers of rapamycin identifies a specific inhibitor of an SCF family E3 ubiquitin ligase [J].

Aghajan, Mariam ;

Jonai, Nao ;

Flick, Karin ;

Fu, Fei ;

Luo, Manlin ;

Cai, Xiaolu ;

Ouni, Ikram ;

Pierce, Nathan ;

Tang, Xiaobo ;

Lomenick, Brett ;

Damoiseaux, Robert ;

Hao, Rui ;

del Moral, Pierre M. ;

Verma, Rati ;

Li, Ying ;

Li, Cheng ;

Houk, Kendall N. ;

Jung, Michael E. ;

Zheng, Ning ;

Huang, Lan ;

Deshaies, Raymond J. ;

Kaiser, Peter ;

Huang, Jing .

NATURE BIOTECHNOLOGY, 2010, 28 (07) :738-U1750

[2] Catalytic enantioselective ring-closing metathesis by a chiral biphen-Mo complex [J].

Alexander, JB ;

La, DS ;

Cefalo, DR ;

Hoveyda, AH ;

Schrock, RR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (16) :4041-4042

[3] Kinetic resolution of chiral α-olefins using optically active ansa-zirconocene polymerization catalysts [J].

Baar, CR ;

Levy, CJ ;

Min, EYJ ;

Henling, LM ;

Day, MW ;

Bercaw, JE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (26) :8216-8231

[4] Highly active chiral ruthenium catalysts for asymmetric cross- and ring-opening cross metathesis [J].

Berlin, Jacob M. ;

Goldberg, Steven D. ;

Grubbs, Robert H. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (45) :7591-7595

[5]

Bielawski C. W., 2009, CONTROLLED LIVING PO, P297, DOI DOI 10.1002/9783527629091.CH6

[6] Living ring-opening metathesis polymerization [J].

Bielawski, Christopher W. ;

Grubbs, Robert H. .

PROGRESS IN POLYMER SCIENCE, 2007, 32 (01) :1-29

[7] Kinetic resolution of racemic α-olefins with ansa-zirconocene polymerization catalysts:: Enantiomorphic site vs. chain end control [J].

Byers, Jeffery A. ;

Bercaw, John E. .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2006, 103 (42) :15303-15308

[8] Norcantharidin reduced cyclins and cytokines production in human peripheral blood mononuclear cells [J].

Chen, Yi-Chun ;

Chang, Shi-Chuan ;

Wu, Ming-Hsi ;

Chuang, Kai-An ;

Wu, Jin-Yi ;

Tsai, Wei-Jern ;

Kuo, Yuh-Chi .

LIFE SCIENCES, 2009, 84 (7-8) :218-226

[9] Catalyst-Dependent Routes to Ring-Opening Metathesis Alternating Copolymers of Substituted Oxanorbornenes and Cyclooctene [J].

Daeffler, Christopher S. ;

Grubbs, Robert H. .

MACROMOLECULES, 2013, 46 (09) :3288-3292

[10] Efficient catalytic enantioselective synthesis of unsaturated amines: Preparation of small- and medium-ring cyclic amines through Mo-catalyzed asymmetric ring-closing metathesis in the absence of solvent [J].

Dolman, SJ ;

Sattely, ES ;

Hoveyda, AH ;

Schrock, RR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (24) :6991-6997

← 1 2 3 4 →