郎建平教授在 Angew. Chem. Int. Ed. 上发表研究论文

Stereoselective Solid-State Synthesis of Substituted Cyclobutanes Assisted by Pseudorotaxane-like MOFs

Fei-Long Hu1,2, YanMi2, Chen Zhu1, Brendan F. Abrahams3, Pierre Braunstein4, and Jian-Ping Lang*,1(郎建平)

  

1 College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu, P. R. China

2 Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi University for Nationalities, Nanning, P. R. China

3 School of Chemistry, University of Melbourne, Victoria, Australia

4 Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, Strasbourg, France

  

Angew. Chem. Int. Ed. 2018, 57, 12696 --12701

  

Regioselective photodimerization of trans4styrylpyridine (4spy) derivatives is performed using pseudorotaxanelike Znbased metal organic frameworks MOFs as templates. The formation of rcttHT (headtotail) dimers is achieved by confining pairs of coordinated 4spy derivative ligands within hexagonal windows and then irradiating them with UV light. It is also possible to achieve a photodimerization reaction where two different substituted 4spy ligands are included in such a MOF material. The ether bond formation is employed to protect the sensitive OH group of HOspy and the methyl group of CH3Ospy is subsequently removed after the formation of cyclobutane derivative in the CH3Ospybased MOF. Introducing substituents at the 2 or 3position of the phenyl group of 4spy does not significantly affect the rate of the dimerization process except in the case of the strongly electronwithdrawing nitro group where the rate is significantly decreased. These results are in striking contrast to the mixtures of photoproducts and low yields obtained by untemplated photodimerization in organic solvents.

  

链接:https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201806076