Abstract
The supporting material on which an asymmetric catalytic reaction takes place has proved to be an important component which could influence the efficiency and sometimes enantioselectivity of a heterogeneous asymmetric reaction. On the other hand, graphene oxide (GO) has attracted broad attentions because of its unique characteristics and potential applications in many fields. However, GOs have been rarely employed as the supporting materials for heterogeneous catalytic reactions, especially those enantioselective reactions. Herein, a new type of GO-based heterogeneous catalyst was prepared for enantioselective addition of diethylzinc to aromatic aldehydes. To produce this GO catalyst, commercial GO was firstly oxidized in an acidic environment to make nanoporous GOs and then enantiopure (R) or (S)-NH2-BINOLs were attached (covalently) onto the nanoporous GOs, and this GO-BINOL was subsequently treated by using Ti(OiPr)4. The as-prepared GO-BINOL-Ti catalyst displayed good reactivity (99%) and modest enantioselectivity (45% ee) in the following asymmetric addition reactions. We expect this preliminary demonstration could inspire the research by using GO as heterogeneous catalytic supports and could improve the enantioselectivity later.
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Gruttadauria M, Giacalone F, Noto R (2008) Supported proline and proline-derivatives as recyclable organocatalysts. Chem Soc Rev 37(8):1666–1688
Wang X, Lu SM, Li J, Liu Y, Li C (2015) Conjugated microporous polymers with chiral binap ligand built-in as efficient catalysts for asymmetric hydrogenation. Catal Sci Technol 5(5):2585–2589
Guo WG, Wang X, Zhang BY, Shen S, Zhou X, Wang P, Liu Y, Li C (2014) Facile synthesis of chiral spirooxindole-based isotetronic acids and 5-1H-Pyrrol-2-ones through cascade reactions with bifunctional organocatalysts. Chem Eur J 20(28):8545–8550
Wang X, Li J, Lu S, Liu Y, Li C (2015) Efficient enantioselective hydrogenation of quinolines catalyzed by conjugated microporous polymers with embedded chiral BINAP ligand. Chin J Catal 36(8):1170–1174
Wang WB, Lu SM, Yang PY, Han XW, Zhou YG (2003) Highly enantioselective iridium-catalyzed hydrogenation of heteroaromatic compounds, quinolines. J Am Chem Soc 125(35):10536–10537
Li C (2004) Chiral synthesis on catalysts immobilized in microporous and mesoporous materials. Catal Rev 46(3–4):419–492
Zhang HD, Zhang YM, Li C (2006) Enantioselective epoxidation of unfunctionalized olefins catalyzed by the Mn(salen) catalysts immobilized in the nanopores of mesoporous materials. J Catal 238(2):369–381
Ding SY, Gao J, Wang Q, Zhang Y, Song WG, Su CY, Wang W (2011) Construction of covalent organic framework for catalysis: Pd/COF-LZU1 in Suzuki-Miyaura coupling reaction. J Am Chem Soc 133(49):19816–19822
Chen H, Müller MB, Gilmore KJ, Wallace GG, Li D (2010) Mechanically strong, electrically conductive, and biocompatible graphene paper. Adv Mater 20(18):3557–3561
Karousis N, Economopoulos SP, Sarantopoulou E, Tagmatarchis N (2010) Porphyrin counter anion in imidazolium-modified graphene-oxide. Carbon 48(3):854–860
Petit C, Bandosz TJ (2010) Enhanced adsorption of ammonia on metal-organic framework/graphite oxide composites: analysis of surface interactions. Adv Funct Mater 20(1):111–118
Xu YX, Bai H, Lu GW, Li C, Shi GQ (2008) Flexible graphene films via the filtration of water-soluble noncovalent functionalized graphene sheets. J Am Chem Soc 130(18):5856–5857
Zhu YW, Murali S, Cai WW, Li XS, Suk JW, Potts JR, Ruoff RS (2010) Graphene and graphene oxide: synthesis, properties, and applications. Adv Mater 22(35):3906–3924
Bonaccorso F, Sun Z, Hasan T, Ferrari AC (2010) Graphene photonics and optoelectronics. Nat Photonics 4(9):611–622
Ma X, Tao H, Yang K, Feng L, Cheng L, Shi X, Li Y, Guo L, Liu Z (2012) A functionalized graphene oxide-iron oxide nanocomposite for magnetically targeted drug delivery, photothermal therapy, and magnetic resonance imaging. Nano Res 5(3):199–212
Hu XG, Mu L, Zhou QX, Wen JP, Pawliszyn J (2011) ssDNA aptamer-based column for simultaneous removal of nanogram per liter level of illicit and analgesic pharmaceuticals in drinking water. Environ Sci Technol 45(11):4890–4895
Pumera M (2011) Graphene-based nanomaterials for energy storage. Energy Environ Sci 4(3):668–674
Sun Y, Wu Q, Shi G (2011) Graphene based new energy materials. Energy Environ Sci 4(4):1113–1132
Han Q, Xia Q, Guo DM, Li C, Fu YZ (2015) Chiral glutamic acid functionalized graphene: preparation and application. Anal Methods-UK 7(13):5387–5390
Kotchey GP, Allen BL, Vedala H, Yanamala N, Kapralov AA, Tyurina YY, Klein-Seetharaman J, Kagan VE, Star A (2011) The enzymatic oxidation of graphene oxide. ACS Nano 5(3):2098–2108
Siamaki AR, Khder AERS, Abdelsayed V, EI-Shall MS, Gupton BF (2011) Microwave-assisted synthesis of palladium nanoparticles supported on graphene: a highly active and recyclable catalyst for carbon-carbon cross-coupling reactions. J Catal 279(1):1–11
Suzuki N, Wang YC, Elvati P, Qu ZB, Kim K, Jiang S, Baumeister E, Lee J, Yeom B, Bahng JH, Lee J, Violi A, Kotov NA (2016) Chiral graphene quantum dots. ACS Nano 10(2):1744–1755
Yeh TF, Chan FF, Hsieh CT, Teng HS (2011) Graphite oxide with different oxygenated levels for hydrogen and oxygen production from water under illumination: the band positions of graphite oxide. J Phys Chem C 115(45):22587–22597
Tan R, Li CY, Luo JQ, Kong Y, Zheng WG (2013) An effective heterogeneous l-proline catalyst for the direct asymmetric aldol reaction using graphene oxide as support. J Catal 298(2):138–147
Nasseri M, Allahresani A, Raissi H (2014) Grafting of a chiral Mn(Ш) complex on graphene oxide nanosheets and its catalytic activity for alkene epoxidation. RSC Adv 4(50):26087–26093
Wu CD, Hu A, Zhang L, Lin W (2005) A homochiral porous metal-organic framework for highly enantioselective heterogeneous asymmetric catalysis. J Am Chem Soc 127(25):8940–8941
Lv N, Xie M, Gu W, Ruan H, Qiu S, Zhou C, Cui Z (2013) Synthesis, properties, and structures of functionalized peri-xanthenoxanthene. Org Lett 15(10):2382–2385
Zheng D, Cao W, Ma H, Ding K (2016) Efficient synthesis of chloromethyl methyl ether and one-pot hydroxyl protection. Chin J Org Chem 36(5):1122–1126
Jankovský O, Nováček M, Luxa J, Sedmidubský D, Fila V, Pumera M, Sofer Z (2016) A new member of the graphene family: graphene acid. Chem Eur J 22(48):17416–17424
Kovtyukhova NI, Ollivier PJ, Martin BR, Mallouk TE, Chizhik SA, Buzaneva EV, Gorchinskiy A (1999) Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations. Chem Mater 11(3):771–778
Ding C, Wei W, Sun H, Ding J, Ren J, Qu X (2014) Reduced graphene oxide supported chiral Ni particles as magnetically reusable and enantioselective catalyst for asymmetric hydrogenation. Carbon 79(1):615–622
Hu X, Mu L, Wen J, Zhou Q (2012) Covalently synthesized graphene oxide-aptamer nanosheets for efficient visible-light photocatalysis of nucleic acids and proteins of viruses. Carbon 50(8):2772–2781
Zheng W, Tan R, Yin S, Zhang Y, Zhao G, Chen Y, Yin D (2015) Ionic liquid-functionalized graphene oxide as an efficient support for the chiral salen Mn(Ш) complex in asymmetric epoxidation of unfunctionalized olefins. Catal Sci Technol 5(4):2092–2102
Cao J, Yin HJ, Song R (2013) Circular dichroism of graphene oxide: the chiral structure model. Front Mater Sci 7(1):83–90
Xu C, Yuan RS, Wang X (2014) Selective reduction of graphene oxide. New Carbon Mater 29(1):61–66
Zhang ZG, Qian H, Longmire J, Zhang XM (2000) Synthesis of chiral bisphosphines with tunable bite angles and their applications in asymmetric hydrogenation of β-Ketoesters. J Org Chem 65(19):6223–6226
Zhang JH, Liao J, Cui X, Yu KB, Zhu J, Deng JG, Zhu SF, Wang LX, Zhou QL, Chung LW, Ye T (2002) Highly efficient and practical resolution of 1,1′-spirobiindane-7,7′-diol by inclusion crystallization with n-benzylcinchonidinium chloride. Tetrahedron-Asymmetry 13(13):1363–1366
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We acknowledge the financial support from the Ministry of Science and Technology of China (No. 2016YFA0203400) and the Chinese Academy of Sciences.
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Wang, X., Guo, J., Qie, F. et al. Enantioselective addition of diethylzinc to aromatic aldehydes catalyzed by chiral BINOL-functionalized nanoporous graphene oxides. J Mater Sci 54, 6908–6916 (2019). https://doi.org/10.1007/s10853-018-03230-9
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DOI: https://doi.org/10.1007/s10853-018-03230-9