CO₂ Adducts of Phosphorus Ylides: Highly Active Organocatalysts for Carbon Dioxide Transformation

Abstract

A series of phosphorus ylide (P-ylide) CO 2 adducts were synthesized and firstly used as organocatalysts for CO 2 transformation. Detailed studies on the cycloaddition reaction of CO 2 with terminal epoxides show that P-ylide CO 2 adducts are efficient metal-free and halogen-free organocatalytsts to mediate this reaction under ambient conditions (25 o C, 1 atm CO 2 ). More importantly, the reactions proceeded with a broad scope, high efficiency, and functional group tolerance and the corresponding cyclic carbonate products were obtained in good to excellent yield (46-99%). Meanwhile, the kinetic study by in-situ FTIR method suggested an intermolecular cooperation effect for effectively accelerating the ring-opening of terminal epoxides. Furthermore, from the investigation on the catalytic diversity of Pylide CO 2 adducts, CO 2 also could be availably converted to functionalized cyclic αalkylidene carbonates, oxazolidinone, N-methylated and N-formylated amines by organocatalytic reactions.

Docking Site Modulation of Isostructural Covalent Organic Frameworks for CO2 Fixation

“…In contrast, heterogeneous catalysts have been widely applied in industry because of easy separation, good recyclability, less catalyst contamination in the products and low cost. Metal organic frameworks (MOFs) have also been explored as efficient heterogeneous catalysts for CO 2 fixation, the harsh conditions needed for such cycloaddition of CO 2 and the instabilities of MOFs in such conditions also ruled out its practical application . Therefore, developing a metal‐free heterogeneous catalyst for efficient conversion of cycloaddition of CO 2 under mild conditions is highly desirable.…”

Assessing the pKa‐Dependent Activity of Hydroxyl Hydrogen Bond Donors in the Organocatalyzed Cycloaddition of Carbon Dioxide to Epoxides: Experimental and Theoretical Study

“…Among several families of organocatalysts, HBDs occupy a prominent position for their ability to activate the reaction substrates by a well-defined array of H-bonds. [11] The cycloaddition reaction can take place under atmospheric conditions, or even from flue gas, [12] when applying several types of catalytic systems including organocatalysts, [5,13] metal-organic complexes [14] coordination compounds [15] and porous organic polymers [16] thus resulting in a potentially sustainable, low-energy intensive process for CO 2 fixation. [8] It leads to industrially relevant cyclic organic carbonates [9] that find increasing application as chemical intermediates [10] and green solvents.…”

Delineation of the Critical Parameters of Salt Catalysts in the N‐Formylation of Amines with CO2

“…F À . [10,11] An umber of salts including [TBA]F, [11] Cs 2 CO 3 , [19] glycine betaine, [40] zwitterionic P-ylide-CO 2 adducts [41] and various carboxylates [42] were proposed to act this way. [10] Based on these observations and the fact that [TBA]F can activate hydrosilanes in the reduction of carbonyls, [35][36][37][38][39] the activity of salt catalysts was attributed to the nucleophilicity of the anion and its ability to activate the hydrosilane reducing agent prior to CO 2 insertion.…”