3068-88-0Relevant articles and documents
Synthesis of β-lactones by the regioselective, cobalt and Lewis acid catalyzed carbonylation of simple and functionalized epoxides
Lee, Jong Tae,Thomas,Alper
, p. 5424 - 5426 (2001)
The PPNCo(CO)4 and BF3·Et2O catalyzed carbonylation of simple and functionalized epoxides in DME gives the corresponding β-lactones regioselectively in good to high yields. The carbonylation occurred selectively at the uns
A covalent triazine framework-based heterogenized Al-Co bimetallic catalyst for the ring-expansion carbonylation of epoxide to β-lactone
Rajendiran, Senkuttuvan,Natarajan, Prakash,Yoon, Sungho
, p. 4635 - 4638 (2017)
Difficulties in product separation and ineffective recycling of the homogenous catalyst deter the mass production of β-lactones via carbonylation of epoxides. Herein, we address these issues, for the first time, using a recyclable heterogenized catalyst [bpy-CTF-Al(OTf)2][Co(CO)4] that efficiently converts propylene oxide (PO) to β-butyrolactone with high selectivity.
Direct Heterogenization of Salphen Coordination Complexes to Porous Organic Polymers: Catalysts for Ring-Expansion Carbonylation of Epoxides
Ganesan, Vinothkumar,Yoon, Sungho
, (2020)
Salen and salphens are important ligands in coordination chemistry due to their ability to form various metal complexes that can be used for a variety of organic transformations. However, salen/salphen complexes are difficult to separate from the reaction mixture, thereby limiting their application to homogeneous systems. Accordingly, considerable effort has been spent to heterogenize the metallosalen/salphen complexes; however, this has resulted in compromised activities and selectivities. Direct heterogenization of metallosalens to form porous organic polymers (POPs) shows promise for heterogeneous catalysis, because it would allow easy separation while retaining catalytic function. Thus, a facile synthetic strategy for preparing metallosalen/salphen-based porous organic polymers through direct molecular knitting using a Friedel-Crafts reaction is presented herein for the first time. As representative candidates, salphenM(III)Cl (M = Al3+ and Cr3+) complexes are knitted by covalent cross-linking using this facile, scalable, one-pot method to synthesize highly POPs in high yields. When incorporated with [Co(CO)4]- anions, the resulting heterogeneous Lewis acidic metal (Al3+ and Cr3+) POPs exhibit propylene oxide ring-expansion carbonylation activity on par with those of their homogeneous counterparts.
Carbonylative Polymerization of Epoxides Mediated by Tri-metallic Complexes: A Dual Catalysis Strategy for Synthesis of Biodegradable Polyhydroxyalkanoates
Li, Wen-Bing,Liu, Ye,Lu, Xiao-Bing,Yang, Jin-Chuang,Yang, Jun
supporting information, (2022/01/20)
Polyhydroxyalkanoates (PHAs) are a unique class of commercially manufactured biodegradable polyesters with properties suitable for partially substituting petroleum-based plastics. However, high costs and low volumes of production have restricted their application as commodity materials. In this study, tri-metallic complexes were developed for carbonylative polymerization via a dual catalysis strategy, and 17 products of novel PHAs with up to 38.2 kg mol?1 Mn values were discovered. The polymerization proceeds in a sequential fashion, which entails the carbonylative ring expansion of epoxide to β-lactone and its subsequent ring-opening polymerization that occurs selectively at the O-alkyl bond via carboxylate species. The wide availability and structural diversity of epoxide monomers provide PHAs with various structures, excellent functionalities, and tunable properties. This study represents a rare example of the preparation of PHAs using epoxides and carbon monoxide as raw materials.
An aluminum(III) picket fence phthalocyanine-based heterogeneous catalyst for ring-expansion carbonylation of epoxides
Jiang, Jianwei,Yoon, Sungho
, p. 6120 - 6125 (2019/03/19)
An effective heterogeneous catalyst for ring-expansion carbonylation of epoxides may have additional advantages over the homogeneous counterpart in terms of facile product separation and recyclability. A new Al(iii) picket fence phthalocyanine complex was synthesized and directly knitted using the Friedel-Crafts reaction to prepare a solid porous network, which was ultimately used to immobilize [Co(CO)4]- ions. The resulting heterogeneous catalyst, [Lewis acid]+[Co(CO)4]-, efficiently catalyzes the conversion of various epoxides into the corresponding β-lactones with high selectivity (99%) and stoichiometric conversion under mild reaction conditions, along with good functional group tolerance.