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Surface-induced formation of stereogenic centers on gold nanoparticles through diastereoselective interfacial Henry reaction: an NMR investigation

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Abstract

This study aims at the synthesis of gold nanoparticles (2–3 nm) functionalized with different nitroalkane-terminated thiols and investigates the chemical reactivity of these confined nitroalkanes towards aldehydes to yield β-nitroalcohols. Interfacial Henry reaction between fixed nitroalkane-terminated thiols with various aromatic and heteroaromatic aldehydes resulted in stereogenic centers on the surface of mixed-monolayer-protected gold nanoparticles (MMPNs). The ratio of the resulting diastereomers was determined by 1H NMR spectroscopy. It was found that some parameters such as the chain length of nitroalkyl and the nature of aromatic aldehyde play the main role in affecting the diastereomeric ratio on the surface of MMPNs. Certain trends have been analyzed from the data, and it can be inferred that some aldehydes approximately prefer the formation of anti diastereomers as the predominant products, while others give syn β-nitroalcohols. We have attributed this stereoselectivity to the packed layers, forceful lateral interactions (van der Waals), and intramolecular hydrogen bonding on the surface of modified gold nanoparticles that are able to suppress the role of solvent and intermolecular interactions.

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Acknowledgments

The authors are grateful to Razi University for their financial support for accomplishment of the work and providing necessary facilities. The authors would like to thank the Dr. Sukhvir Bhangu for her valuable comments to improve the quality of the paper. G. Abdi is also thankful to the Iran Nanotechnology Initiative Council (INIC) for their partial support on this project.

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Authors and Affiliations

  1. Department of Organic Chemistry, Faculty of Chemistry, Razi University, Kermanshah, 6714967346, Iran

    Gisya Abdi & Abdolhamid Alizadeh

  2. Nanoscience & Nanotechnology Research Center (NNRC), Razi University, Kermanshah, 6714967346, Iran

    Abdolhamid Alizadeh

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  1. Gisya Abdi
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  2. Abdolhamid Alizadeh
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Correspondence to Abdolhamid Alizadeh.

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Abdi, G., Alizadeh, A. Surface-induced formation of stereogenic centers on gold nanoparticles through diastereoselective interfacial Henry reaction: an NMR investigation. Gold Bull 51, 65–74 (2018). https://doi.org/10.1007/s13404-018-0232-5

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