Amphiphilic Hyperbranched Polyethoxysiloxane: A Self-Templating Assembled Platform to Fabricate Functionalized Mesostructured Silicas for Aqueous Enantioselective Reactions

被引:24
作者
Zhang, Kun [1 ]
An, Juzeng [1 ]
Su, Yanchao [1 ]
Zhang, Jueyu [1 ]
Wang, Ziyun [1 ]
Cheng, Tanyu [1 ]
Liu, Guohua [1 ]
机构
[1] Shanghai Normal Univ, Shanghai Key Lab Rare Earth Funct Mat, Minist Educ, Key Lab Resource Chem, Shanghai 200234, Peoples R China
来源
ACS CATALYSIS | 2016年 / 6卷 / 09期
关键词
asymmetric catalysis; heterogeneous catalyst; immobilization; mesoporous material; silica; ASYMMETRIC TRANSFER HYDROGENATION; TRANSITION-METAL-COMPLEXES; MICHAEL ADDITION; MESOPOROUS SILICA; AROMATIC KETONES; ALPHA-AMINOPHOSPHONATES; CONJUGATE ADDITION; CHIRAL SQUARAMIDE; WATER; CATALYSTS;
D O I
10.1021/acscatal.6b01315
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Fabrication of amphiphilic mesostructured silica as a heterogeneous catalyst is beneficial to facilitate an aqueous reaction due to its highly dispersed nature in water. In this work, by taking advantage of a self-templating assembled strategy, we construct two types of mesostructured silicas as heterogeneous catalysts, chiral ruthenium/diamine-functionalized and chiral cinchonine-based squaramide-functionalized heterogeneous catalysts, through the use of amphiphilic poly(ethylene glycol) monomethyl ether-modified hyper branched polyethoxysiloxane as a silica precursor. As presented in the study, the chiral ruthenium/diamine-functionalized catalyst performs an asymmetric transfer hydrogenation of acyclic alpha-trifluoromethylimines to chiral alpha-trifluoromethylamines in water, whereas the chiral squaramide-functionalized catalyst enables efficiently asymmetric Michael addition of acetylacetone to nitroalkenes in brine. Both highly catalytic performances are attributed to the combined multifunctionalities of well-defined single-site chiral active species, highly dispersed catalytic centers, and practical phase-transferred function. Furthermore, both catalysts can also be recovered easily and reused repeatedly for at least seven times without loss of catalytic activity. Such a feature makes this self-templating assembly attractive for construction of various heterogeneous catalysts.
引用
收藏
页码:6229 / 6235
页数:7
相关论文
共 77 条
[1]   Pd-catalyzed asymmetric hydrogenation of α-fluorinated iminoesters in fluorinated alcohol:: A new and catalytic enantioselective synthesis of fluoro α-amino acid derivatives [J].
Abe, H ;
Amii, H ;
Uneyama, K .
ORGANIC LETTERS, 2001, 3 (03) :313-315
[2]   Microgel-Based Adaptive Hybrid Capsules with Tunable Shell Permeability [J].
Agrawal, Garima ;
Uelpenich, Andreas ;
Zhu, Xiaomin ;
Moeller, Martin ;
Pich, Andrij .
CHEMISTRY OF MATERIALS, 2014, 26 (20) :5882-5891
[3]   Hydrogen bonding mediated enantioselective organocatalysis in brine: significant rate acceleration and enhanced stereoselectivity in enantioselective Michael addition reactions of 1,3-dicarbonyls to β-nitroolefins [J].
Bae, Han Yong ;
Some, Surajit ;
Oh, Joong Suk ;
Lee, Yong Seop ;
Song, Choong Eui .
CHEMICAL COMMUNICATIONS, 2011, 47 (34) :9621-9623
[4]   Enhancement of catalytic performance in asymmetric transfer hydrogenation by microenvironment engineering of the nanocage [J].
Bai, Shiyang ;
Yang, Hengquan ;
Wang, Peng ;
Gao, Jinsuo ;
Li, Bo ;
Yang, Qihua ;
Li, Can .
CHEMICAL COMMUNICATIONS, 2010, 46 (43) :8145-8147
[5]   Unexpected Inversions in Asymmetric Reactions: Reactions with Chiral Metal Complexes, Chiral Organocatalysts, and Heterogeneous Chiral Catalysts [J].
Bartok, Mihaly .
CHEMICAL REVIEWS, 2010, 110 (03) :1663-1705
[6]   Enantioselective synthesis of α-nitro-δ-ketosulfones via a quinine-squaramide catalyzed conjugate addition of α-nitrosulfones to enones [J].
Bera, Kalisankar ;
Namboothiri, Irishi N. N. .
CHEMICAL COMMUNICATIONS, 2013, 49 (90) :10632-10634
[7]   Multiple Core-Shell Functionalized Colloidal Mesoporous Silica Nanoparticles [J].
Cauda, Valentina ;
Schlossbauer, Axel ;
Kecht, Johann ;
Zuerner, Andreas ;
Bein, Thomas .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (32) :11361-11370
[8]   Enantioselective Pd-Catalyzed Hydrogenation of Fluorinated Imines: Facile Access to Chiral Fluorinated Amines [J].
Chen, Mu-Wang ;
Duan, Ying ;
Chen, Qing-An ;
Wang, Duo-Sheng ;
Yu, Chang-Bin ;
Zhou, Yong-Gui .
ORGANIC LETTERS, 2010, 12 (21) :5075-5077
[9]   Silica-Supported Chiral Catalysts for Asymmetric Transfer Hydrogenation [J].
Cheng, Tanyu ;
Zhao, Qiankun ;
Zhang, Dacheng ;
Liu, Guohua .
CURRENT ORGANIC CHEMISTRY, 2015, 19 (08) :667-680
[10]   Transition-metal-functionalized ordered mesoporous silicas: an overview of sustainable chiral catalysts for enantioselective transformations [J].
Cheng, Tanyu ;
Zhao, Qiankun ;
Zhang, Dacheng ;
Liu, Guohua .
GREEN CHEMISTRY, 2015, 17 (04) :2100-2122