Synthesis of Cyclic Carbonates from Alkenyl and Alkynyl Substrates

Abstract

As an extensively used chemical product, cyclic carbonate was generally synthesized by transesterification, or the cycloaddition of epoxides, diols with CO2. To reduce the production costs and expand the raw materials, alkenyl and alkynyl substrates have caused much attention in the synthesis of cyclic carbonates, such as olefins, allyl alcohols and propargylic alcohols. Based on the alkenyl substrate, the synthetic process involves a continuous reaction of oxidative carboxylation, with epoxide or halohydrin as an intermediate usually. Therefore, peroxides and nucleophiles (halogens or organic bases) are often necessary in the conversion. Using propargylic alcohols to produce α‐alkylidene cyclic carbonates, noble metal catalysts play crucial roles in alkynyl activation, and organic bases are considered to assist the intramolecular and intermolecular proton transfer and combine CO2 molecular. As the carboxyl sources in products, inorganic carbonates and organic carboxylic acids also have some applications instead of CO2. In this review, we summarized the synthetic routes of cyclic carbonates from alkenyl and alkynyl substrates in the aspect of catalyst, mechanism and the development tendency.

Organocatalytic Regioselective Synthesis of Sulfur-Containing N-Alkyl Carbamates from Alkyne-Derived Cyclic Carbonates

“…All the reactions showed >99% production of regioisomer A, which indicated that the steric hindrance of these secondary amines is favourable to the regioselective ring-opening of DPMOD. Compared with 4-methylpiperidine (12), the use of 13 caused lower conversion of DPMOD (72%), while 12 led to a 100% conversion of DPMOD. It is reasonable that the methyl group of 12 was more electron-donating than the hydroxyl group of 13 and thus improved the reactivity of 12 towards DPMOD.…”

“…[7,8] As an inert C1 compound, CO 2 is usually converted to the five-membered cyclic carbonate via the coupling reaction with alkyne derivatives or epoxides that are high-energy compounds. [9][10][11][12] Followed by ring-opening addition reaction with amines, these cyclic carbonates can be effectively converted to the urethane compounds. This reaction is the basic chemistry of the non-isocyanate route for making polyurethanes (PUs).…”

Mesoporous Silica-Supported Ionic Liquids as Catalysts for Styrene Carbonate Synthesis from CO2

“…A wide spectrum of compounds have been studied as catalysts for this synthesis, both homogeneous and heterogeneous, as well as immobilized ones, such as onium quaternary salts [3][4][5][6], metal complexes [7][8][9][10], metal-organic frameworks [11,12], and ionic liquids [13][14][15][16][17]. However, the direct synthesis of cyclic carbonates from CO 2 and olefin as raw materials is of growing interest [18,19]. This process, i.e., an oxidative carboxylation of olefins with CO 2 , proceeds in two stages.…”

“…In this regard, the immobilization of homogeneous catalysts on the surface of organic or inorganic supports are of particular interest. Examples of the use of immobilized catalysts in the direct synthesis of cyclic carbonates can be found in the literature [18,19].…”

Anionic Copolymerization of Carbonyl Sulfide with Epoxides via Alkali Metal Alkoxides

“…The utilization of one-carbon (C1) compounds such as carbon dioxide (CO 2 ) to make polymers has drawn much attention in the past few decades. [1][2][3][4][5][6][7][8][9][10][11][12][13] As a sulfur analogue of CO 2 , carbon sulfide (COS) is a by-product in the process of burning fossil fuels or coal gas, or the corruption of livings. It causes acid rain, ozonosphere damage [14] and haze [15] by a series of photochemical reactions.…”