Direct synthesis of organic carbonates by oxidative carboxylation of olefins catalyzed by metal oxides: developing green chemistry based on carbon dioxide

Abstract

In this paper we report on the 'oxidativecarboxylation' of olefins catalysed by either transition metal complexes or metal oxides. We discuss the oxidation mechanism under homogeneous and heterogeneous conditions. In the former case the process is driven by co-ordination to the metal centre, in the latter a radical reaction takes place. The yield of carbonate is strongly dependent on the catalyst used. Copyright #

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities

“…Carbonates, (RO) 2 CO (8), can also be prepared by inserting CO 2 into O-H bonds followed by dehydration or by oxidative carboxylation of olefins. 132 This synthetic approach has the possibility of providing a new route to compounds that have very large potential markets.…”

Synthesis of Cyclic Carbonates from Alkenyl and Alkynyl Substrates

“…Using Nb 2 O 5 and high pressure O 2 -CO 2 mixture, about 4.5% product was generated, accompanied by highly selective byproducts, benzaldehyde and benzoic acid. [17] In a later study, NbCl 5 was added as co-catalyst and the yield of styrene carbonate was improved to 11%. [42] The product distribution was proven to be strongly influenced by the solvent, O 2 -CO 2 pressure and reaction temperature.…”

“…However, developing halogen-free processes is of positive significance on reducing the pollution to environment and the corrosion to equipment. Besides the metal oxides reported by Aresta [17] and the Fe 3 ＋ -doped g-C 3 N 4 / SBA-15, [60] Duan [69] prepared a ZnW 12 -based MOF catalyst for the direct synthesis of styrene carbonates (Figure 2). The basic groups on ligands contributed to CO 2 capture and conversion.…”

“…However, mixed products with low selectivity were usually obtained. Afterwards, Aresta [16,17] reported direct synthesis of styrene carbonate from styrene, O 2 and CO 2 with Rh(I) and metal oxide catalysts, which gave low yields (10%-20%). In view of the low epoxidation selectivity of O 2 to olefins, organic and inorganic peroxides were investigated, such as t-butyl hydroperoxide (TBHP), [18][19][20] H 2 O 2 , [21] m-chloroperbenzoic acid (m-CPBA) [22] and urea hydrogen peroxide (UHP).…”

Oxidative Carboxylation of 1-Decene to 1,2-Decylene Carbonate

“…However, the epoxidation and the cycloaddition of CO 2 to an epoxide has been mainly studied separately and only a limited amount of literature is available for an integrated approach [3,[7][8][9][10][11][12][13][14][15][16][17][18][19]. Most of these studies used tert-butyl hydroperoxide (TBHP) [3,10,13,14,[16][17][18] or hydrogen peroxide [9,10,17,19] as the oxidant.…”