Covalent Functionalization of Nanodiamonds by Ruthenium Porphyrin, and Their Catalytic Activity in the Cyclopropanation Reaction of Olefins

Chiara Lorecchio,Laura Lazzarini,Pietro Tagliatesta,Robertino Zanoni,Emanuela Tamburri,Silvia Orlanducci

doi:10.3390/catal10060666

Abstract

Detonation nanodiamonds (DNDs) were functionalized by ruthenium porphyrins and used as catalysts in the cyclopropanation reaction of olefins. The heterogeneous catalyst was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and XPS (X-ray photoelectron spectroscopy). The XPS was used to control the binding of the ruthenium porphyrin to the DNDs’ surface. This catalyst was used in the cyclopropanation reactions of simple olefins and was reused with no loss of activity in four consecutive cycles, after recovering each time by simple centrifugation.

Highlights

The cyclopropyl ring is present in a number of interesting natural products
[2] Synthetic iron, rhodium and osmium porphyrins have been reported as catalysts for the cyclopropanation reaction of simple olefins by ethyldiazoacetate (EDA). [3,4,5,6,7] Compared to copper salts, like CuCl, which gives the anti isomers, some porphyrin catalysts are able to reverse the syn/anti ratio of the products, depending on the nature of the metal
[8] Recently, in our laboratory we have been involved in researching the catalytic oxidation of alkenes, the cyclooligomerization of alkynes, and the cyclopropanation of olefins catalyzed by metalloporphyrins [9,10,11]

Summary

Introduction

The cyclopropyl ring is present in a number of interesting natural products. [2] Synthetic iron, rhodium and osmium porphyrins have been reported as catalysts for the cyclopropanation reaction of simple olefins by ethyldiazoacetate (EDA). [8] Recently, in our laboratory we have been involved in researching the catalytic oxidation of alkenes, the cyclooligomerization of alkynes, and the cyclopropanation of olefins catalyzed by metalloporphyrins [9,10,11]. This last reaction was extensively investigated, developing iron [12] and rhodium [13] meso-tetraphenylporphyrin catalysts used in the homogeneous phase. Several papers have reported the cyclopropanation reactions of α-substituted styrenes, 1,3-dienes and some terminal alkenes by diazoacetates, catalyzed by metalloporphyrin complexes. [16,17,18,19,20] The choice of the metal, and the possibility of varying both its Catalysts 2020, 10, 666; doi:10.3390/catal10060666 www.mdpi.com/journal/catalysts

Methods

Results

Discussion

Conclusion