Journal Home > Volume 14 , Issue 2
Nano Research 2021, 14(2): 466-472 https://doi.org/10.1007/s12274-020-2905-7
Research Article | Issue | Published: 25 June 2020

Chiral metal-organic frameworks with tunable catalytic selectivity in asymmetric transfer hydrogenation reactions

Show Author's Information Xu Chen1,  Zhiwei Qiao2,  Bang Hou1,  Hong Jiang1,  Wei Gong1,  Jinqiao Dong1,  Hai-Yang Li3,  Yong Cui1,  Yan Liu1,( )
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China
Guangzhou Key Laboratory for New Energy and Green Catalysis, School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China
Green Catalysis Center and College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China
Keywords:
metal-organic frameworks, metal phosphonate, Lewis acid, asymmetric catalysis, hydrogenation reaction
Topics:
Catalysis Catalyst activityCatalyst selectivity Ligands Metal ionsMetalsOrganic frameworks OrganometallicsPrecious metals
Cite this article:
Chen X, Qiao Z, Hou B, et al. Chiral metal-organic frameworks with tunable catalytic selectivity in asymmetric transfer hydrogenation reactions. Nano Research, 2021, 14(2): 466-472. https://doi.org/10.1007/s12274-020-2905-7
Download citation
EndNote(RIS)
BibTeX

579

Views

25

Downloads

Citations

33

Crossref

N/A

WoS

35

Scopus

4

CSCD

Abstract Full text Electronic supplementary material About this article

Metal-organic frameworks (MOFs) have achieved great success in the field of heterogeneous catalysis, however, it’s still challenging to design MOF catalysts with enhanced selectivity. Here, we demonstrated a combination strategy of metal design and ligand design on the enantioselectivity—that is the enantioselectivities of chiral MOF (CMOF) catalysts could be significantly enhanced by the rational choice of metal ions with higher electronegativities and introducing sterically demanding groups into the ligands. Four isostructural Ca-, Sr- and Zn-based CMOFs were prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 2,4,6-trimethyl- and 2,4,6-trifluoro-phenyl groups at the 3,3'-position. The uniformly distributed metal phosphonates along the channels could act as Lewis acids and catalyze the asymmetric transfer hydrogenation of heteroaromatic imines (benzoxazines and quinolines). Particularly, the Ca-based MOF 1 with 2,4,6-trimethyl groups at the substituents exhibited enhanced catalytic performance, affording the highest enantioselectivity (up to 97%). It is also the first report of the heterogeneous catalyst with chiral non-noble metal phosphonate active sites for asymmetric transfer hydrogenation reactions with Hantzsch ester as the hydrogen source. The catalyst design strategy demonstrated here is expected to develop new types of chiral materials for asymmetric catalysis and other chiral applications.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Chiral metal-organic frameworks with tunable catalytic selectivity in asymmetric transfer hydrogenation reactions

Show Author's information Xu Chen1, Zhiwei Qiao2, Bang Hou1, Hong Jiang1, Wei Gong1, Jinqiao Dong1, Hai-Yang Li3, Yong Cui1, Yan Liu1,( )
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China
Guangzhou Key Laboratory for New Energy and Green Catalysis, School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China
Green Catalysis Center and College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China

Abstract

Metal-organic frameworks (MOFs) have achieved great success in the field of heterogeneous catalysis, however, it’s still challenging to design MOF catalysts with enhanced selectivity. Here, we demonstrated a combination strategy of metal design and ligand design on the enantioselectivity—that is the enantioselectivities of chiral MOF (CMOF) catalysts could be significantly enhanced by the rational choice of metal ions with higher electronegativities and introducing sterically demanding groups into the ligands. Four isostructural Ca-, Sr- and Zn-based CMOFs were prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 2,4,6-trimethyl- and 2,4,6-trifluoro-phenyl groups at the 3,3'-position. The uniformly distributed metal phosphonates along the channels could act as Lewis acids and catalyze the asymmetric transfer hydrogenation of heteroaromatic imines (benzoxazines and quinolines). Particularly, the Ca-based MOF 1 with 2,4,6-trimethyl groups at the substituents exhibited enhanced catalytic performance, affording the highest enantioselectivity (up to 97%). It is also the first report of the heterogeneous catalyst with chiral non-noble metal phosphonate active sites for asymmetric transfer hydrogenation reactions with Hantzsch ester as the hydrogen source. The catalyst design strategy demonstrated here is expected to develop new types of chiral materials for asymmetric catalysis and other chiral applications.

Keywords: metal-organic frameworks, metal phosphonate, Lewis acid, asymmetric catalysis, hydrogenation reaction

References(47)

[1]
F. Su,; Y. H. Guo, Advancements in solid acid catalysts for biodiesel production. Green Chem. 2014, 16, 2934-2957.
Google Scholar
[2]
J. Liang,; Z. B. Liang,; R. Q. Zou,; Y. L. Zhao, Heterogeneous catalysis in zeolites, mesoporous silica, and metal-organic frameworks. Adv. Mater. 2017, 29, 1701139.
Google Scholar
[3]
A. H. Chughtai,; N. Ahmad,; H. A. Younus,; A. Laypkov,; F. Verpoort, Metal-organic frameworks: Versatile heterogeneous catalysts for efficient catalytic organic transformations. Chem. Soc. Rev. 2015, 44, 6804-6849.
Google Scholar
[4]
A. Yadav,; P. Kanoo, Metal-organic frameworks as platform for Lewis-acid-catalyzed organic transformations. Chem.—Asian J. 2019, 14, 3531-3551.
Google Scholar
[5]
C. Wang,; D. M. Liu,; W. B. Lin, Metal-organic frameworks as a tunable platform for designing functional molecular materials. J. Am. Chem. Soc. 2013, 135, 13222-13234.
Google Scholar
[6]
X. Chen,; Y. W. Peng,; X. Han,; Y. Liu,; X. C. Lin,; Y. Cui, Sixteen isostructural phosphonate metal-organic frameworks with controlled Lewis acidity and chemical stability for asymmetric catalysis. Nat. Commun. 2017, 8, 2171.
Google Scholar
[7]
X. Chen,; H. Jiang,; B. Hou,; W. Gong,; Y. Liu,; Y. Cui, Boosting chemical stability, catalytic activity and enantioselectivity of metal-organic frameworks for batch and flow reactions. J. Am. Chem. Soc. 2017, 139, 13476-13482.
Google Scholar
[8]
X. Chen,; H. Jiang,; X. Li,; B. Hou,; W. Gong,; X. W. Wu,; X. Han,; F. F. Zheng,; Y. Liu,; J. W. Jiang, et al. Chiral phosphoric acids in metal-organic frameworks with enhanced acidity and tunable catalytic selectivity. Angew. Chem., Int. Ed. 2019, 58, 14748-14757.
Google Scholar
[9]
Z. Y. Li,; A. W. Peters,; A. E. Platero-Prats,; J. Liu,; C. W. Kung,; H. Noh,; M. R. DeStefano,; N. M. Schweitzer,; K. W. Chapman,; J. T. Hupp, et al. Fine-tuning the activity of metal-organic framework-supported cobalt catalysts for the oxidative dehydrogenation of propane. J. Am. Chem. Soc. 2017, 139, 15251-15258.
Google Scholar
[10]
N. Huang,; S. Yuan,; H. Drake,; X. Y. Yang,; J. D. Pang,; J. S. Qin,; J. L. Li,; Y. M. Zhang,; Q. Wang,; D. L. Jiang, et al. Systematic engineering of single substitution in zirconium metal-organic frameworks toward high-performance catalysis. J. Am. Chem. Soc. 2017, 139, 18590-18597.
Google Scholar
[11]
J. A. Johnson,; B. M. Petersen,; A. Kormos,; E. Echeverría,; Y. S. Chen,; J. Zhang, A new approach to non-coordinating anions: Lewis acid enhancement of porphyrin metal centers in a zwitterionic metal-organic framework. J. Am. Chem. Soc. 2016, 138, 10293-10298.
Google Scholar
[12]
R. J. C. Dubey,; R. J. Comito,; Z. W. Wu,; G. H. Zhang,; A. J. Rieth,; C. H. Hendon,; J. T. Miller,; M. Dinca, Highly stereoselective heterogeneous diene polymerization by Co-MFU-4l: A single-site catalyst prepared by cation exchange. J. Am. Chem. Soc. 2017, 139, 12664-12669.
Google Scholar
[13]
K. Gedrich,; M. Heitbaum,; A. Notzon,; I. Senkovska,; R. Fröhlich,; J. Getzschmann,; U. Mueller,; F. Glorius,; S. Kaskel, A family of chiral metal-organic frameworks. Chem.—Eur. J. 2011, 17, 2099-2106.
Google Scholar
[14]
L. Q. Ma,; J. M. Falkowski,; C. Abney,; W. B. Lin, A series of isoreticular chiral metal-organic frameworks as a tunable platform for asymmetric catalysis. Nat. Chem. 2010, 2, 838-846.
Google Scholar
[15]
C. X. Tan,; X. Han,; Z. J. Li,; Y. Liu,; Y. Cui, Controlled exchange of achiral linkers with chiral linkers in Zr-based UiO-68 metal-organic framework. J. Am. Chem. Soc. 2018, 140, 16229-16236.
Google Scholar
[16]
W. Gong,; X. Chen,; H. Jiang,; D. D. Chu,; Y. Cui,; Y. Liu, Highly stable Zr(IV)-based metal-organic frameworks with chiral phosphoric acids for catalytic asymmetric tandem reactions. J. Am. Chem. Soc. 2019, 141, 7498-7508.
Google Scholar
[17]
M. Banerjee,; S. Das,; M. Yoon,; H. J. Choi,; M. H. Hyun,; S. M. Park,; G. Seo,; K. Kim, Postsynthetic modification switches an achiral framework to catalytically active homochiral metal-organic porous materials. J. Am. Chem. Soc. 2009, 131, 7524-7525.
Google Scholar
[18]
J. M. Falkowski,; T. Sawano,; T. Zhang,; G. Tsun,; Y. Chen,; J. V. Lockard,; W. B. Lin, Privileged phosphine-based metal-organic frameworks for broad-scope asymmetric catalysis. J. Am. Chem. Soc. 2014, 136, 5213-5216.
Google Scholar
[19]
P. F. Ji,; X. Y. Feng,; P. Oliveres,; Z. Li,; A. Murakami,; C. Wang,; W. B. Lin, Strongly Lewis acidic metal-organic frameworks for continuous flow catalysis. J. Am. Chem. Soc. 2019, 141, 14878-14888.
Google Scholar
[20]
P. F. Ji,; T. Drake,; A. Murakami,; P. Oliveres,; J. H. Skone,; W. B. Lin, Tuning Lewis acidity of metal-organic frameworks via perfluorination of bridging ligands: Spectroscopic, theoretical, and catalytic studies. J. Am. Chem. Soc. 2018, 140, 10553-10561.
Google Scholar
[21]
Y. Zhang,; J. Guo,; L. Shi,; Y. F. Zhu,; K. Hou,; Y. L. Zheng,; Z. Y. Tang, Tunable chiral metal organic frameworks toward visible light-driven asymmetric catalysis. Sci. Adv. 2017, 3, e1701162.
Google Scholar
[22]
D. Parmar,; E. Sugiono,; S. Raja,; M. Rueping, Complete field guide to asymmetric BINOL-phosphate derived Brønsted acid and metal catalysis: History and classification by mode of activation; Brønsted acidity, hydrogen bonding, ion pairing, and metal phosphates. Chem. Rev. 2014, 114, 9047-9153.
Google Scholar
[23]
A. Parra,; S. Reboredo,; A. M. M. Castro,; J. Alemán, Metallic organophosphates as catalysts in asymmetric synthesis: A return journey. Org. Biomol. Chem. 2012, 10, 5001-5020.
Google Scholar
[24]
F. Foubelo,; M. Yus, Catalytic asymmetric transfer hydrogenation of imines: Recent advances. Chem. Rec. 2015, 15, 907-924.
Google Scholar
[25]
C. Zheng,; S. L. You, Transfer hydrogenation with Hantzsch esters and related organic hydride donors. Chem. Soc. Rev. 2012, 41, 2498-2518.
Google Scholar
[26]
M. Rueping,; A. P. Antonchick,; T. Theissmann, Remarkably low catalyst loading in Brønsted acid catalyzed transfer hydrogenations: Enantioselective reduction of benzoxazines, benzothiazines, and benzoxazinones. Angew. Chem., Int. Ed. 2006, 45, 6751-6755.
Google Scholar
[27]
Y. L. Zhang,; R. Zhao,; R. L. Y. Bao,; L. Shi, Highly enantioselective SPINOL-derived phosphoric acid catalyzed transfer hydrogenation of diverse C=N-containing heterocycles. Eur. J. Org. Chem. 2015, 2015, 3344-3351.
Google Scholar
[28]
X. F. Tu,; L. Z. Gong, Highly enantioselective transfer hydrogenation of quinolines catalyzed by gold phosphates: Achiral ligand tuning and chiral-anion control of stereoselectivity. Angew. Chem., Int. Ed. 2012, 51, 11346-11349.
Google Scholar
[29]
C. Bleschke,; J. Schmidt,; D. S. Kundu,; S. Blechert,; A. Thomas, A chiral microporous polymer network as asymmetric heterogeneous organocatalyst. Adv. Synth. Catal. 2011, 353, 3101-3106.
Google Scholar
[30]
D. S. Kundu,; J. Schmidt,; C. Bleschke,; A. Thomas,; S. Blechert, A microporous binol-derived phosphoric acid. Angew. Chem., Int. Ed. 2012, 51, 5456-5459.
Google Scholar
[31]
Z. X. Zhang,; Y. R. Ji,; L. Wojtas,; W. Y. Gao,; S. Q. Ma,; M. J. Zaworotko,; J. C. Antilla, Two homochiral organocatalytic metal organic materials with nanoscopic channels. Chem. Commun. 2013, 49, 7693-7695.
Google Scholar
[32]
J. H. Xie,; S. F. Zhu,; Q. L. Zhou, Transition metal-catalyzed enantioselective hydrogenation of enamines and imines. Chem. Rev. 2011, 111, 1713-1760.
Google Scholar
[33]
N. Arai,; Y. Saruwatari,; K. Isobe,; T. Ohkuma, Asymmetric hydrogenation of quinoxalines, benzoxazines, and a benzothiazine catalyzed by chiral ruthenabicyclic complexes. Adv. Synth. Catal. 2013, 355, 2769-2774.
Google Scholar
[34]
C. Wang,; C. Q. Li,; X. F. Wu,; A. Pettman,; J. L. Xiao, pH-regulated asymmetric transfer hydrogenation of quinolines in water. Angew. Chem., Int. Ed. 2009, 48, 6524-6528.
Google Scholar
[35]
J. L. Núñez-Rico,; A. Vidal-Ferran, [Ir(P-OP)]-catalyzed asymmetric hydrogenation of diversely substituted C=N-containing heterocycles. Org. Lett. 2013, 15, 2066-2069.
Google Scholar
[36]
S. Fleischer,; S. L. Zhou,; S. Werkmeister,; K. Junge,; M. Beller, Cooperative iron-Brønsted acid catalysis: Enantioselective hydrogenation of quinoxalines and 2H-1,4-benzoxazines. Chem.—Eur. J. 2013, 19, 4997-5003.
Google Scholar
[37]
A. L. Spek, Single-crystal structure validation with the program PLATON. J. Appl. Cryst. 2003, 36, 7-13.
Google Scholar
[38]
Z. P. Chen,; Y. G. Zhou, Asymmetric hydrogenation of heteroarenes with multiple heteroatoms. Synthesis 2016, 48, 1769-1781.
Google Scholar
[39]
M. Breuer,; K. Ditrich,; T. Habicher,; B. Hauer,; M. Keßeler,; R. Stürmer,; T. Zelinski, Industrial methods for the production of optically active intermediates. Angew. Chem., Int. Ed. 2004, 43, 788-824.
Google Scholar
[40]
E. Vitaku,; D. T. Smith,; J. T. Njardarson, Analysis of the structural diversity, substitution patterns, and frequency of nitrogen heterocycles among U.S. FDA approved pharmaceuticals. J. Med. Chem. 2014, 57, 10257-10274.
Google Scholar
[41]
R. G. Pearson, Absolute electronegativity and hardness: Application to inorganic chemistry. Inorg. Chem. 1988, 27, 734-740.
Google Scholar
[42]
S. M. Chen,; H. X. Wang,; Z. J. Li,; F. L. Wei,; H. Zhu,; S. Q. Xu,; J. X. Xu,; J. J. Liu,; H. Gebru,; K. Guo, Metallic organophosphate catalyzed bulk ring-opening polymerization. Polym. Chem. 2018, 9, 732-742.
Google Scholar
[43]
J. Wang,; M. W. Chen,; Y. Ji,; S. B. Hu,; Y. G. Zhou, Kinetic resolution of axially chiral 5- or 8-substituted quinolines via asymmetric transfer hydrogenation. J. Am. Chem. Soc. 2016, 138, 10413-10416.
Google Scholar
[44]
D. B. Zhao,; F. Glorius, Enantioselective hydrogenation of isoquinolines. Angew. Chem., Int. Ed. 2013, 52, 9616-9618.
Google Scholar
[45]
A. Alix,; C. Lalli,; P. Retailleau,; G. Masson, Highly enantioselective electrophilic α-bromination of enecarbamates: Chiral phosphoric acid and calcium phosphate salt catalysts. J. Am. Chem. Soc. 2012, 134, 10389-10392.
Google Scholar
[46]
I. Ibáñez,; M. Kaneko,; Y. Kamei,; R. Tsutsumi,; M. Yamanaka,; T. Akiyama, Enantioselective friedel-crafts alkylation reaction of indoles with α-trifluoromethylated β-nitrostyrenes catalyzed by chiral BINOL metal phosphate. ACS Catal. 2019, 9, 6903-6909.
Google Scholar
[47]
C. Lalli,; A. Dumoulin,; C. Lebée,; F. Drouet,; V. Guérineau,; D. Touboul,; V. Gandon,; J. P. Zhu,; G. Masson, Chiral calcium-BINOL phosphate catalyzed diastereo- and enantioselective synthesis of syn-1,2-disubstituted 1,2-diamines: Scope and mechanistic studies. Chem.—Eur. J. 2015, 21, 1704-1712.
Google Scholar
File
12274_2020_2905_MOESM1_ESM.pdf (9.6 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 15 February 2020
Revised: 26 May 2020
Accepted: 28 May 2020
Published: 25 June 2020
Issue date: February 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 91956124, 21875136, 21620102001, 91856204, 21978058 and 21676094), the National Key Basic Research Program of China (No. 2016YFA0203400), Key Project of Basic Research of Shanghai (Nos. 17JC1403100, 18JC1413200 and 19JC1412600) and Shanghai Rising-Star Program (No. 19QA1404300).

Return