Privileged Phosphine-Based Metal-Organic Frameworks for Broad-Scope Asymmetric Catalysis

被引:229
作者
Falkowski, Joseph M. [1 ]
Sawano, Takahiro [1 ]
Zhang, Teng [1 ]
Tsun, Galen [2 ]
Chen, Yuan [3 ]
Lockard, Jenny V. [3 ]
Lin, Wenbin [1 ]
机构
[1] Univ Chicago, Dept Chem, Chicago, IL 60637 USA
[2] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA
[3] Rutgers State Univ, Dept Chem, Newark, NJ 07102 USA
基金
美国国家科学基金会;
关键词
HYBRID SOLIDS; HYDROGENATION; BINAP; 1,4-ADDITION; ACIDS; ARYL;
D O I
10.1021/ja500090y
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A robust and porous Zr metal-organic framework (MOF) based on a BINAP-derived dicarboxylate linker, BINAP-MOF, was synthesized and post-synthetically metalated with Ru and Rh complexes to afford highly enantioselective catalysts for important organic transformations. The Rh-functionalized MOF is not only highly enantioselective (up to >99% ee) but also 3 times as active as the homogeneous control. XAFS studies revealed that the Ru-functionalized MOF contains Ru-BINAP precatalysts with the same. coordination environment as the homogeneous Ru complex. The post-synthetically metalated BINAP-MOFs provide a versatile family of single-site solid catalysts for catalyzing a broad scope of asymmetric organic transformations, including addition of aryl and alkyl groups to alpha,beta-unsaturated ketones and hydrogenation of substituted alkene and carbonyl compounds.
引用
收藏
页码:5213 / 5216
页数:4
相关论文
共 42 条
[1]   A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability [J].
Cavka, Jasmina Hafizovic ;
Jakobsen, Soren ;
Olsbye, Unni ;
Guillou, Nathalie ;
Lamberti, Carlo ;
Bordiga, Silvia ;
Lillerud, Karl Petter .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (42) :13850-13851
[2]   A metal-organic framework material that functions as an enantioselective catalyst for olefin epoxidation [J].
Cho, So-Hye ;
Ma, Baoqing ;
Nguyen, SonBinh T. ;
Hupp, Joseph T. ;
Albrecht-Schmitt, Thomas E. .
CHEMICAL COMMUNICATIONS, 2006, (24) :2563-2565
[3]   Postsynthetic Methods for the Functionalization of Metal-Organic Frameworks [J].
Cohen, Seth M. .
CHEMICAL REVIEWS, 2012, 112 (02) :970-1000
[4]   Functional Mixed Metal-Organic Frameworks with Metalloligands [J].
Das, Madhab C. ;
Xiang, Shengchang ;
Zhang, Zhangjing ;
Chen, Banglin .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (45) :10510-10520
[5]   Crystal engineering of NLO materials based on metal-organic coordination networks [J].
Evans, OR ;
Lin, WB .
ACCOUNTS OF CHEMICAL RESEARCH, 2002, 35 (07) :511-522
[6]   Chiral porous solids based on lamellar lanthanide phosphonates [J].
Evans, OR ;
Ngo, HL ;
Lin, WB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (42) :10395-10396
[7]   Metal-Organic Frameworks as Single-Site Solid Catalysts for Asymmetric Reactions [J].
Falkowski, Joseph M. ;
Liu, Sophie ;
Lin, Wenbin .
ISRAEL JOURNAL OF CHEMISTRY, 2012, 52 (07) :591-603
[8]   Actuation of Asymmetric Cyclopropanation Catalysts: Reversible Single-Crystal to Single-Crystal Reduction of Metal-Organic Frameworks [J].
Falkowski, Joseph M. ;
Wang, Cheng ;
Liu, Sophie ;
Lin, Wenbin .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (37) :8674-8678
[9]   Crystallized frameworks with giant pores:: Are there limits to the possible? [J].
Férey, G ;
Mellot-Draznieks, C ;
Serre, C ;
Millange, F .
ACCOUNTS OF CHEMICAL RESEARCH, 2005, 38 (04) :217-225
[10]   The Chemistry and Applications of Metal-Organic Frameworks [J].
Furukawa, Hiroyasu ;
Cordova, Kyle E. ;
O'Keeffe, Michael ;
Yaghi, Omar M. .
SCIENCE, 2013, 341 (6149) :974-+