Subtopic Deep Dive

← Carbon dioxide utilization in catalysis

CO2 Cycloaddition to Epoxides for Cyclic Carbonates
Research Guide

What is CO2 Cycloaddition to Epoxides for Cyclic Carbonates?

CO2 cycloaddition to epoxides produces five-membered cyclic carbonates using metal or organocatalysts.

This reaction couples CO2 with epoxides to form cyclic carbonates serving as green solvents and polymer precursors. Catalysts include metal-organic frameworks (MOFs), porphyrins, and ionic liquids, emphasizing mild conditions and recyclability. Over 10 highly cited papers exist, with Darensbourg (1996) at 802 citations.

Curated Papers

Key Challenges

Why It Matters

Cyclic carbonates replace phosgene-based processes, enabling CO2 utilization for sustainable chemical production. Hf-NU-1000 MOF by Beyzavi et al. (2014, 508 citations) achieves high efficiency in epoxide activation under mild conditions. Bifunctional porphyrin catalysts by Ema et al. (2014, 456 citations) enable solvent-free synthesis, advancing industrial scalability. MOF-5/n-Bu4NBr by Song et al. (2009, 468 citations) demonstrates heterogeneous catalysis for propylene oxide conversion.

Key Research Challenges

Mild Condition Catalysis

Achieving high yields at ambient temperature and pressure remains difficult without sacrificial reagents. Song et al. (2009, 468 citations) used MOF-5/n-Bu4NBr for propylene oxide at mild conditions. Ema et al. (2014, 456 citations) optimized porphyrin counteranions for solvent-free reactions.

Catalyst Recyclability

Heterogeneous catalysts must retain activity over multiple cycles without leaching. Beyzavi et al. (2014, 508 citations) reported Hf-NU-1000's stability in epoxide cycloaddition. Liang et al. (2016, 401 citations) developed reusable Meim-UiO-66 for CO2-epoxide coupling.

Broad Substrate Scope

Extending to internal epoxides and functional groups challenges selectivity. Darensbourg (1996, 802 citations) reviewed catalyst limitations for diverse epoxides. Xie et al. (2013, 761 citations) showed conjugated microporous polymers handling various substrates at ambient conditions.

Essential Papers

Catalysts for the reactions of epoxides and carbon dioxide

Donald J. Darensbourg · 1996 · Coordination Chemistry Reviews · 802 citations

Capture and conversion of CO2 at ambient conditions by a conjugated microporous polymer

Yong Xie, Tingting Wang, Xiaohuan Liu et al. · 2013 · Nature Communications · 761 citations

Ring-opening copolymerization (ROCOP): synthesis and properties of polyesters and polycarbonates

Shyeni Paul, Yunqing Zhu, Charles Romain et al. · 2015 · Chemical Communications · 565 citations

This feature article highlights the opportunities presented by ring-opening copolymerization (ROCOP) as a controlled route to prepare polyesters and polycarbonates.

Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆

Christine Jérôme, Philippe Lecomte · 2008 · Advanced Drug Delivery Reviews · 555 citations

A Hafnium-Based Metal–Organic Framework as an Efficient and Multifunctional Catalyst for Facile CO<sub>2</sub> Fixation and Regioselective and Enantioretentive Epoxide Activation

M. Hassan Beyzavi, Rachel C. Klet, Samat Tussupbayev et al. · 2014 · Journal of the American Chemical Society · 508 citations

Porous heterogeneous catalysts play a pivotal role in the chemical industry. Herein a new Hf-based metal-organic framework (Hf-NU-1000) incorporating Hf6 clusters is reported. It demonstrates high ...

MOF-5/n-Bu4NBr: an efficient catalyst system for the synthesis of cyclic carbonates from epoxides and CO2 under mild conditions

Jinliang Song, Zhaofu Zhang, Suqin Hu et al. · 2009 · Green Chemistry · 468 citations

The development of efficient heterogeneous catalysts for the cycloaddition of CO2 with epoxides to produce five-membered cyclic carbonates under mild reaction conditions is of great importance. In ...

Bifunctional Porphyrin Catalysts for the Synthesis of Cyclic Carbonates from Epoxides and CO<sub>2</sub>: Structural Optimization and Mechanistic Study

Tadashi Ema, Yuki Miyazaki, Junta Shimonishi et al. · 2014 · Journal of the American Chemical Society · 456 citations

We prepared bifunctional Mg(II) porphyrin catalysts 1 for the solvent-free synthesis of cyclic carbonates from epoxides and CO2. The activities of 1d, 1h, and 1i, which have Br(-), Cl(-), and I(-) ...

Reading Guide

Foundational Papers

Start with Darensbourg (1996, 802 citations) for catalyst fundamentals, then Beyzavi et al. (2014, 508 citations) for Hf-NU-1000's epoxide activation benchmarks.

Recent Advances

Study Ema et al. (2014, 456 citations) for porphyrin optimization and Liang et al. (2016, 401 citations) for imidazolium-UiO-66 recyclability advances.

Core Methods

Lewis acid activation of epoxides with halide nucleophiles (Darensbourg 1996); bifunctional H-bonding in porphyrins (Ema 2014); postsynthetic MOF ionization (Liang 2016).

How PapersFlow Helps You Research CO2 Cycloaddition to Epoxides for Cyclic Carbonates

Discover & Search

Research Agent uses citationGraph on Darensbourg (1996, 802 citations) to map 800+ related works on epoxide-CO2 catalysts, then findSimilarPapers to uncover MOF variants like Song et al. (2009). exaSearch queries 'CO2 epoxide cycloaddition MOF recyclability' for 250M+ OpenAlex papers, surfacing Liang et al. (2016).

Analyze & Verify

Analysis Agent applies readPaperContent to Ema et al. (2014) for bifunctional porphyrin mechanisms, then verifyResponse (CoVe) cross-checks yield claims against Beyzavi et al. (2014). runPythonAnalysis extracts turnover frequencies from tables in Song et al. (2009) using pandas for statistical comparison, with GRADE scoring evidence strength.

Synthesize & Write

Synthesis Agent detects gaps in recyclability data across Darensbourg (1996) and recent MOF papers, flagging contradictions in mild-condition claims. Writing Agent uses latexEditText and latexSyncCitations to draft reaction schemes with Ema et al. (2014) refs, latexCompile for PDF, and exportMermaid for cycloaddition mechanism diagrams.

Use Cases

"Compare catalyst TOFs for CO2-epoxide cycloaddition in MOFs vs porphyrins"

Research Agent → searchPapers + citationGraph → Analysis Agent → readPaperContent (Song 2009, Ema 2014) → runPythonAnalysis (pandas TOF extraction/plot) → matplotlib yield comparison chart.

"Write LaTeX review section on Hf-NU-1000 for cyclic carbonate synthesis"

Synthesis Agent → gap detection (Beyzavi 2014) → Writing Agent → latexEditText (draft) → latexSyncCitations (add Darensbourg 1996) → latexCompile → PDF with embedded scheme.

"Find GitHub repos with code for modeling CO2-epoxide reaction kinetics"

Research Agent → paperExtractUrls (Xie 2013) → paperFindGithubRepo → githubRepoInspect (kinetics simulators) → runPythonAnalysis (test repo code in sandbox).

Automated Workflows

Deep Research workflow scans 50+ papers from Darensbourg (1996) citationGraph, producing structured report on catalyst evolution with GRADE-verified metrics. DeepScan applies 7-step CoVe to Ema et al. (2014) mechanisms, checkpointing halide effects. Theorizer generates hypotheses on porphyrin-MOF hybrids from Song et al. (2009) and Liang et al. (2016) data.

Try Doxa for CO2 Cycloaddition to Epoxides for Cyclic Carbonates Research

Frequently Asked Questions

What defines CO2 cycloaddition to epoxides?

It is the [3+2] coupling of CO2 with epoxides to form five-membered cyclic carbonates, catalyzed by Lewis acids and nucleophiles.

What are key catalyst types?

Metal-organic frameworks (Beyzavi et al. 2014; Song et al. 2009), bifunctional porphyrins (Ema et al. 2014), and conjugated polymers (Xie et al. 2013) enable mild conditions.

What are foundational papers?

Darensbourg (1996, 802 citations) reviews early catalysts; Xie et al. (2013, 761 citations) demonstrates ambient conversion with microporous polymers.

What are open problems?

Scalable catalysts for internal epoxides without co-catalysts; metal-free systems with >99% selectivity under 1 atm CO2, per gaps in Ema et al. (2014) and Liang et al. (2016).