Nitro-Coordinated Polyoxometalate Catalyst for Selective Alkene Cleavage

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Solution Overview

Problem

Current methods for the selective cleavage of carbon-carbon double bonds in alkenes to produce aldehydes and ketones are non-selective and require harsh oxidizing conditions, limiting their industrial applicability and efficiency, especially when using renewable carbon sources.

Innovation Solution

A process utilizing a nitro-coordinated polyoxometalate catalyst, specifically a polyoxoanion salt with a transition metal, to catalyze the carbon-carbon bond cleavage of alkenes, generating aldehydes and ketones, where the catalyst is formed in situ or independently using nitrogen dioxide or nitroalkanes under aerobic conditions.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If strong oxidizing conditions are used to cleave carbon-carbon double bonds, then high yields of carboxylic acids are obtained, but selective preparation of aldehydes is prevented

Engineering Contradiction:
ImproveyieldVSAvoidselectivity
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The invention changes the oxidation state parameters by using mild oxidizing conditions (molecular oxygen) instead of strong oxidants, and controls the reaction pathway through catalytic species (silver or gold) to achieve aldehyde formation without over-oxidation to carboxylic acids

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention introduces metal catalysts (silver or gold) as intermediaries that facilitate the selective oxidation of alkenes to aldehydes using molecular oxygen, preventing direct strong oxidation that would lead to carboxylic acids

Inventive Principle:
Principle #24Intermediary (Mediator)

2Ease of operation

If free radical autooxidation mechanisms are used with molecular oxygen, then the reaction proceeds under mild conditions, but non-selective product formation occurs

Engineering Contradiction:
Improvereaction conditionsVSAvoidselectivity
Core Design Contradiction:
Ease of operationVSManufacturing precision

Solution Approach 1:

The invention introduces metal catalysts (silver or gold) as intermediaries that facilitate the selective oxidation of alkenes to aldehydes using molecular oxygen, preventing direct strong oxidation that would lead to carboxylic acids

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention changes the reaction mechanism parameters by using coordinated molecular oxygen and controlled radical pathways through metal catalysts, achieving both mild conditions and high selectivity for aldehyde formation

Inventive Principle:
Principle #35Parameter changes

3Manufacturing precision

If multistep reaction cascades are used (epoxidation and hydrolysis), then aldehydes can be prepared selectively, but process complexity increases

Engineering Contradiction:
ImproveselectivityVSAvoidprocess steps
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The invention merges multiple reaction steps (oxidation and cleavage) into a single catalytic process using silver or gold catalysts with molecular oxygen, achieving aldehyde formation without separate epoxidation and hydrolysis steps

Inventive Principle:
Principle #5Merging (Combining)

Solution Approach 2:

The invention introduces metal catalysts (silver or gold) as intermediaries that facilitate the selective oxidation of alkenes to aldehydes using molecular oxygen, preventing direct strong oxidation that would lead to carboxylic acids

Inventive Principle:
Principle #24Intermediary (Mediator)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This process achieves high yields of aldehydes and ketones with improved selectivity and efficiency, suitable for industrial applications, using renewable carbon sources and avoiding the need for harsh oxidizing conditions.

Implementation Method 1

a process for preparing aldehydes and ketones by carbon-carbon bond cleavage of alkenes, wherein the process is catalysed by a first row transition metal nitro coordinated polyoxometalate catalyst

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

The aerobic cleavage of carbon-carbon double bonds of alkenes, especially to aldehydes, is a valuable transformation of synthetic importance

Methodology Applied
Scientific EffectOxidation: Oxidation

Data Source

PatentEP3113877B1Preparation of aldehydes and ketones from alkenes using polyoxometalate catalysts and nitrogen oxides
Publication Date: 2023.10.11 YEDA RES & DEV CO LTD
  • EP3113877B1 patent drawingFigure 1~2
  • EP3113877B1 patent drawingFigure 3~4
  • EP3113877B1 patent drawingFigure 5

AI summary

The present invention relates to a process for preparing aldehydes and ketones by carbon- carbon bond cleavage of alkenes, wherein the process is catalysed by first row transition metal nitro coordinated polyoxometalate catalyst. The catalyst can be prepared by pre-treatment of aqua coordinated polyoxometalates with NO2, or they are formed in situ when the reactions are carried in nitroalkanes under aerobic conditions, or they are formed in situ from nitrosyl (NO) compounds in the presence of O2.