Aryl Thiol Ester Synthesis via Copper-Catalyzed Sandmeyer Coupling
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Solution Overview
Problem
Current methods for synthesizing aryl thiol ester compounds often require harsh reaction conditions and result in low yields, necessitating the development of a more efficient production method capable of producing these compounds under mild conditions with high yield.
Innovation Solution
The method involves a Sandmeyer-type coupling reaction using a diazonium compound and a thioate compound with a transition metal complex catalyst, specifically a copper complex, to rapidly synthesize aryl thiol ester compounds under mild conditions, typically between 0 to 40°C, with yields improved by using a copper complex catalyst.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Ease of manufacture
If conventional nucleophilic reaction of thiolate with carboxylic acid derivative is used, then aryl thiol ester compound can be synthesized, but harsh reaction conditions are required
Solution Approach 1:
The invention changes the reaction parameters by using diazonium compounds instead of conventional carboxylic acid derivatives, enabling the reaction to proceed under mild conditions (room temperature, aqueous or alcoholic solvents) while maintaining synthesis feasibility through the Sandmeyer-type coupling mechanism
2Ease of manufacture
If thermal rearrangement of O-arylthioesters is used, then aryl thiol ester compound can be synthesized, but harsh reaction conditions are required
Solution Approach 1:
The invention changes the reaction parameters from thermal rearrangement conditions to mild coupling conditions using diazonium compounds, achieving both mild reaction conditions and high productivity through the catalytic Sandmeyer-type coupling reaction that proceeds rapidly at room temperature
3Ease of manufacture
If electrophilic substrate reacts with organometallic catalyst, then aryl thiol ester compound can be synthesized, but harsh reaction conditions are required
Solution Approach 1:
The invention changes the reaction parameters by using diazonium compounds as electrophilic substrates with simple copper catalysts instead of complex organometallic catalysts, achieving mild reaction conditions while reducing catalyst complexity and making the process more industrially viable
4Ease of manufacture
If Sandmeyer-type coupling reaction without catalyst is used, then aryl thiol ester compound can be synthesized under mild conditions, but yield is low (40-60%)
Solution Approach 1:
The invention introduces copper catalysts as intermediaries in the Sandmeyer-type coupling reaction, which mediate the reaction between diazonium compounds and thiolates to significantly improve the yield from 40-60% to over 80%, while maintaining the mild reaction conditions
Solution Approach 2:
The invention optimizes reaction parameters by selecting appropriate copper catalysts (CuI, CuBr, CuCl) and ligands (phenanthroline, bipyridine) to enhance the reaction efficiency and yield, while maintaining room temperature operation and using simple solvents
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 efficiently synthesizes aryl thiol ester compounds with high yields, making them suitable intermediates for organic compounds, pharmaceuticals, and other materials, while maintaining mild reaction conditions.
Implementation Method 1
a Sandmeyer-type coupling reaction using a catalyst... the catalyst is a transition metal complex... the transition metal complex is a copper complex
Data Source
AI summary
The present invention provides a production method capable of synthesizing an aryl thiol ester compound under mild conditions rapidly at a high yield. The present invention provides a method for producing an aryl thiol ester compound including producing an aryl thiol ester compound represented by the following general formula (1) from a diazonium compound represented by the following general formula (2) and a thioate compound represented by the following general formula (3) by a Sandmeyer-type coupling reaction using a catalyst, [wherein A1 and A2 are each independently an optionally substituted aryl group or an optionally substituted heteroaryl group; X1 is a monovalent anion; and M1 is a monovalent cation].