Investigations on organozinc compounds XIV. Organozinc-catalyzed polymerization of lactones. The interaction between ethylzinc methoxide and (ethylzinc)diphenylamine and β-propiolactone

Chemical Routes for the Transformation of Biomass into Chemicals

“…Poly-3-hydroxypropionic acid has been prepared by the condensation of 3HP esters and by the ring-opening polymerization of β-propiolactone catalyzed by acids, bases, or salts. − The ring-opening polymerization of β-propiolactone is most adequate since generally it provides a greater degree of control of molecular weight and co-monomer incorporation. However, the main drawbacks of β-propiolactone are its carcinogenic character and the difficulty of its large-scale synthesis. − An alternative route to the ring-opening polymerization of β-propiolactone for the preparation of high-weight poly-3-hydroxypropionic acid is the ring-opening polymerization of macrocyclic esters which can be directly obtained from 3HPA .…”

“…224,225 Poly-3-hydroxypropionic acid has been prepared by the condensation of 3HP esters 226 and by the ring-opening polymerization of β-propiolactone catalyzed by acids, bases, or salts. [227][228][229][230][231] The ring-opening polymerization of β-propiolactone is most adequate since generally it provides a greater degree of control of molecular weight and co-monomer incorporation. However, the main drawbacks of β-propiolactone are its carcinogenic character and the difficulty of its large-scale synthesis.…”

Single-Site β-Diiminate Zinc Catalysts for the Alternating Copolymerization of CO2 and Epoxides: Catalyst Synthesis and Unprecedented Polymerization Activity

“…Assuming that metal carboxylates would mimic the reactivity of the potentially unstable metal carbonates, we commenced the design and synthesis of well-defined complexes of the form L n MOR (R ) alkyl, acyl). Since zinc compounds exhibit high activities for both lactone polymerizations 3,4,[32][33][34][35][36][37] and CO 2 /epoxide reactions, [23][24][25][26][27][28][29][30] we decided to initially investigate the synthesis and application of complexes of the form L n ZnOR. We reasoned the ideal ligands for such complexes would be synthesized easily from readily available starting materials, and systematic ligand variation would allow the investigation of both steric and electronic parameters on the polymerization reaction.…”

Pentanuclear Complexes for a Series of Alkylzinc Carboxylates

“…Zinc carboxylate interactions are common in biology, where they perform key roles in metabolic processes . Zinc carboxylate complexes are also important catalysts for various functional group transformations and polymerizations, − and recently, they have attracted attention as structural units in metal-organic polymers (MOPs) and frameworks (MOFs). − Alkylzinc carboxylates in particular, of the general form [RZn(OOCR′)], have been studied as catalysts for the copolymerization of CO 2 with epoxides, as modified Smith−Simmons reagents for cyclopropanation reactions, and as efficient precursors for zinc oxocarboxylates (Zn 4 O(OOCR) 6 ) and zinc sulfidocarboxylates, which can subsequently be used as building units for high-porosity MOFs for chemical storage applications …”