Organic Macrocycle Synthesis via COF Clip-Off Chemistry
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Solution Overview
Problem
Existing methods struggle to synthesize organic macrocycles with high purity and yield, particularly those containing reactive functional groups, due to competing reactions and complex purification steps.
Innovation Solution
The use of clip-off chemistry to selectively disassemble covalent organic frameworks (COFs) by strategically positioning resistant and sensitive bonds, allowing for the controlled formation of macrocycles with reactive functional groups.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Productivity
If traditional synthesis methods are used to create organic macrocycles, then bond formation can be achieved, but the synthetic yield remains low and purity is compromised due to competing intermolecular reactions and polymerization
Solution Approach 1:
The patent segments the macrocycle synthesis approach by first constructing a discrete molecular precursor with specific functional groups, then using clip-off chemistry to selectively break bonds and release the macrocycle. This segmentation prevents intermolecular polymerization by working with discrete molecules rather than allowing uncontrolled bond formation between multiple molecules, thereby improving both yield and purity.
Solution Approach 2:
The patent applies preliminary action by pre-forming the molecular precursor structure before the actual macrocycle release. The precursor is designed with specific bond types that can be selectively broken later, allowing all necessary atomic arrangements to be in place before the final cleavage step, thus avoiding competing reactions during the critical bond formation phase.
2Productivity
If conventional bond formation methods are used, then macrocycles can be synthesized, but complex purification steps are required to separate from linear polymeric side-products
Solution Approach 1:
The patent extracts the macrocycle from the precursor structure through selective bond breaking. By designing the precursor with specific cleavable bonds, the macrocycle can be extracted as a pure product without needing to separate it from polymeric side-products, eliminating complex purification steps and improving synthesis efficiency.
Solution Approach 2:
The patent converts the potential harm of bond breaking (which could lead to random fragmentation) into a benefit by using selective bond breaking. The clip-off chemistry approach allows controlled breaking of specific bonds in the precursor to release the macrocycle, transforming what could be a harmful random process into a beneficial selective release mechanism that improves purity and efficiency.
3Manufacturing precision
If traditional cyclization methods are used, then macrocycles can be formed, but regio- and stereoselectivity control is difficult to achieve
Solution Approach 1:
The patent applies local quality by designing the precursor molecule with specific local features - particular bond types positioned at specific locations that are selective for breaking. This allows precise control over which bonds break and where the macrocycle forms, achieving high regio- and stereoselectivity without complex synthetic pathways.
Solution Approach 2:
Instead of building the macrocycle through complex cyclization reactions and then trying to control selectivity, the patent inverts the approach: it creates a precursor structure and then uses selective bond breaking to release the macrocycle. This inversion simplifies the pathway while achieving precise control over the final structure.
4Manufacturing precision
If macrocycles with reactive functional groups are synthesized by direct methods, then the desired structure can be obtained, but competing reactions occur and purity is reduced
Solution Approach 1:
The patent uses preliminary action by forming the precursor structure with reactive functional groups already in place before the final cleavage step. This allows the reactive groups to be protected during precursor formation and then released in a controlled manner, preventing competing reactions that would occur if reactive groups were present during bond formation steps.
Solution Approach 2:
The precursor structure acts as an intermediary that carries the reactive functional groups in a protected state. The clip-off chemistry step serves as an intermediary mechanism that selectively breaks bonds to release the macrocycle with its reactive groups intact, preventing direct competition between the reactive groups and other molecules during synthesis.
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 approach enables the synthesis of organic macrocycles with high selectivity, yield, and purity, overcoming the challenges of traditional methods by reducing synthetic degrees of freedom and avoiding intermolecular reactions.
Implementation Method 1
The synthesis of organic molecules encompasses thousands of methodologies to create new bonds, giving rise to a myriad of compounds, both new and well-known, that find application across various fields, including pharmaceutical, materials science, or agrochemicals.
Implementation Method 2
use of clip-off chemistry as a synthetic strategy to selectively create new molecules and materials, in particular through the programmed disassembly of crystalline reticular structures, in particular covalent organic frameworks
Data Source
Figure 1~2b
Figure 3
Figure 4a~5
AI summary
The present invention refers to a process for preparing a specific organic macrocycle (I), which comprises disassembling a covalent organic framework via clip-off chemistry, which comprises submitting the framework to a bond-breaking reaction to yield a specific macrocycle having equal functional groups. The present invention also refers to the specific organic macrocycles (I1) - (I8).