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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.
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页码:5213 / 5216
页数:4
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