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
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
收藏
页码:102 / 104
页数:3
相关论文
共 32 条
[11]   Asymmetric ring-closing metathesis: Kinetic resolution catalyzed by a chiral molybdenum alkylidene complex [J].
Fujimura, O ;
Grubbs, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (10) :2499-2500
[12]   Highly active chiral ruthenium catalysts for asymmetric ring-closing olefin metathesis [J].
Funk, TW ;
Berlin, JM ;
Grubbs, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (06) :1840-1846
[13]   Enantioselective Synthesis of [7]Helicene: Dramatic Effects of Olefin Additives and Aromatic Solvents in Asymmetric Olefin Metathesis [J].
Grandbois, Alain ;
Collins, Shawn K. .
CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (30) :9323-9329
[14]   Enantioselective Polymerization of Epoxides: A Highly Active and Selective Catalyst for the Preparation of Stereoregular Polyethers and Enantiopure Epoxides [J].
Hirahata, Wataru ;
Thomas, Renee M. ;
Lobkovsky, Emil B. ;
Coates, Geoffrey W. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (52) :17658-+
[15]   The ROMP toolbox upgraded [J].
Leitgeb, Anita ;
Wappel, Julia ;
Slugovc, Christian .
POLYMER, 2010, 51 (14) :2927-2946
[16]   Catalyst site epimerization during the kinetic resolution of chiral α-olefins by polymerization [J].
Min, Endy Y. -J. ;
Byers, Jeffery A. ;
Bercaw, John E. .
ORGANOMETALLICS, 2008, 27 (10) :2179-2188
[17]   Metallocene-mediated asymmetric coordination polymerization of polar vinyl monomers to optically active, stereoregular polymers [J].
Miyake, Garret M. ;
Chen, Eugene Y. -X. .
MACROMOLECULES, 2008, 41 (10) :3405-3416
[18]   THE RING-OPENING METATHESIS POLYMERIZATION OF 7-OXABICYCLO[2.2.1]HEPT-5-ENE DERIVATIVES - A NEW ACYCLIC POLYMERIC IONOPHORE [J].
NOVAK, BM ;
GRUBBS, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (03) :960-961
[19]   Kinetic resolution of planar-chiral ferrocenes by molybdenum-catalyzed enantioselective metathesis [J].
Ogasawara, Masamichi ;
Watanabe, Susumu ;
Fan, Liyan ;
Nakajima, Kiyohiko ;
Takahashi, Tamotsu .
ORGANOMETALLICS, 2006, 25 (22) :5201-5203
[20]   Kinetic Resolution of Planar-Chiral (?6-Arene)Chromium Complexes by Molybdenum-Catalyzed Asymmetric Ring-Closing Metathesis [J].
Ogasawara, Masamichi ;
Wu, Wei-Yi ;
Arae, Sachie ;
Watanabe, Susumu ;
Morita, Tomotaka ;
Takahashi, Tamotsu ;
Kamikawa, Ken .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (12) :2951-2955