Rhodium Porphyrin Bound to a Merrifield Resin as Heterogeneous Catalyst for the Cyclopropanation Reaction of Olefins

Abstract

Abstract:Cyclopropanation reaction is an important tool for obtaining interesting compounds and can be catalyzed by metalloporphyrins with high syn/anti ratio. The catalyst cannot be recycled and is usually lost during chromatographic separation from the two isomeric products. In this paper a meso-tetraphenylporphyrin rhodium(III) chloride was bound to a Merrifield resin and used to catalyze the cyclopropanation reaction of nine olefins, giving good yields and selectivities of the final products and for the first time, a partial recycling of the catalyst. This new catalytic system will be tested in the future for the synthesis of natural products containing cyclopropyl ring.

[Rh(L-alaninate)(1,5-Cyclooctadiene)] Catalyzed Helix-Sense-Selective Polymerizations of Achiral Phenylacetylenes

“…The coordination of L-alanine to rhodium is supported. When L-alanine was coordinated to rhodium, the chemical shift of the olefinic and methylene protons in cod changed from 4.45, 2.43, and 1.99 ppm (Figure 1A) to 3.89, 2.29, and 1.69 ppm (Figure 1B), respectively [6]. The coordination of cod to rhodium is also supported.…”

“…Asymmetric catalysis is one of the best methods for the synthesis of optically active organic compounds [1,2]. The design and development of novel catalytic systems for asymmetric synthesis and polymerizations have been active research areas in recent years [3,4,5,6,7,8,9,10]. In particular, in the field of phenylacetylene ( PA ) asymmetric polymerizations, Rh catalysts have been found to play a vital role and cannot be replaced by other metal catalysts [11].…”

Carbene Transfer Reactions Catalysed by Dyes of the Metalloporphyrin Group

“…Tagliatesta and co-workers reported a heterogeneous system based on a meso -tetraphenylporphyrin rhodium(III) chloride, bound to a Merrifield resin ( Figure 4 ), to catalyse the cyclopropanation reaction of several olefins, giving good yields for the final products. The linkage between the Rh(III) porphyrin and the solid support allowed the separation of the functionalized resin from the reaction mixtures by vacuum filtration and further reuse, although with significant loss of activity in the second cycle [ 59 ].…”

A Computational Study on the Mechanism of Catalytic Cyclopropanation Reaction with Cobalt N-Confused Porphyrin: The Effects of Inner Carbon and Intramolecular Axial Ligand

“…Among such metalloporphyrin-catalyzed reactions, carbene transfer to olefins has been developed to synthesize cyclopropane rings, essential structural motifs found in biologically active natural products and drug molecules [ 6 , 7 ]. So far, a variety of metalloporphyrin complexes (Rh [ 8 , 9 ], Os [ 10 ], Fe [ 11 , 12 ], Ru [ 10 , 13 , 14 ], Ir [ 15 ], Co [ 16 , 17 ], etc.) have been demonstrated to be effective for catalytic cyclopropanation reactions.…”