Periodic Reporting for period 1 - GASGOLD (Gold(I)-Catalyzed Polymerization of Acetylene Gas)
Reporting period: 2022-09-01 to 2024-08-31
Acetylene is an inexpensive gaseous reagent that is a major feedstock for chemical synthesis. The small size of acetylene provides a high atom economical potential, well suited for the growing demands of environmentally friendly and financially viable synthetic protocols. The synthesis of 1,3-dienes and oligomeric/polymeric derivatives, such as polyacetylene are examples of current important industrial applications of acetylene. The catalysts used for these processes often struggle with inefficiency and other issues. Acetylene is also highly underutilized in more elaborate organic transformations, such as those catalyzed by transition metals. The incorporation of acetylene as a feedstock in a wider synthetic context will, due to its unique abilities and potential, help tackle current societal environmental and economic challenges.
GASGOLD proposes the development of efficient Au(I)-catalyzed methodologies for challenging intermolecular reactions with acetylene to form a range of novel vinylated molecules and important monomers, oligomers and polymers under simple and mild experimental conditions. The success of this project offers innovative solutions and alternative methods to generate previously unobtainable C–C and C–O bonds, in addition to a general improvement of the important transition metal mediated reactions with acetylene, such as the synthesis of 1,3-dienes.
Acetylene is a highly important feedstock for chemical industry, with it being used as a starting material for the synthesis of materials such as synthetic rubbers, elastomers and polymer resins. The underutilization of acetylene in more elaborate organic transformations stems from a lack of existing protocols successfully employing acetylene, rather than a supply shortage, with the global demand of acetylene in 2020 being 1.9 million metric tons and it experiences continuous growth. The successful application of acetylene in attractive and innovative synthetic methodologies will provide significant upsides to current synthetic tools due to the low cost, high atom economy and unique reactivity of acetylene.
The synthesis of substituted 1,3-dienes have been established using a range of transition metal catalysts, by many of these protocols require harsh reaction conditions, high catalyst loadings, long reaction times and expensive starting materials. Therefore, there is a high demand for methods of the selective synthesis of 1,3-butadiene and other substituted dienes from inexpensive starting materials, such as acetylene gas.
GASGOLD aims to generalize and expand on the application of acetylene in transition metal catalyzed methodologies for the challenging application in Au(I)-catalyzed intermolecular cascade synthesis of a range of organic scaffolds stemming from substrates such as alkenes and alcohols. It also aims to improve on the synthesis of 1,3-dienes and related oligomers through divergent reactivity of reaction intermediates formed through the aforementioned Au(I)-catalyzed reaction of acetylene and alkenes.
GASGOLD proposes the development of efficient Au(I)-catalyzed methodologies for challenging intermolecular reactions with acetylene to form a range of novel vinylated molecules and important monomers, oligomers and polymers under simple and mild experimental conditions. The success of this project offers innovative solutions and alternative methods to generate previously unobtainable C–C and C–O bonds, in addition to a general improvement of the important transition metal mediated reactions with acetylene, such as the synthesis of 1,3-dienes.
Acetylene is a highly important feedstock for chemical industry, with it being used as a starting material for the synthesis of materials such as synthetic rubbers, elastomers and polymer resins. The underutilization of acetylene in more elaborate organic transformations stems from a lack of existing protocols successfully employing acetylene, rather than a supply shortage, with the global demand of acetylene in 2020 being 1.9 million metric tons and it experiences continuous growth. The successful application of acetylene in attractive and innovative synthetic methodologies will provide significant upsides to current synthetic tools due to the low cost, high atom economy and unique reactivity of acetylene.
The synthesis of substituted 1,3-dienes have been established using a range of transition metal catalysts, by many of these protocols require harsh reaction conditions, high catalyst loadings, long reaction times and expensive starting materials. Therefore, there is a high demand for methods of the selective synthesis of 1,3-butadiene and other substituted dienes from inexpensive starting materials, such as acetylene gas.
GASGOLD aims to generalize and expand on the application of acetylene in transition metal catalyzed methodologies for the challenging application in Au(I)-catalyzed intermolecular cascade synthesis of a range of organic scaffolds stemming from substrates such as alkenes and alcohols. It also aims to improve on the synthesis of 1,3-dienes and related oligomers through divergent reactivity of reaction intermediates formed through the aforementioned Au(I)-catalyzed reaction of acetylene and alkenes.
GASGOLD has accomplished the development on new methodologies which successfully employs acetylene to synthesize a range of different molecular scaffolds. The synthesis of novel 3-vinyl chromanes have been published and includes the first example of enantioselective activation of acetylene by Au(I). The resulting exocyclic alkene provided for a good handle for further diversification of the products. The synthesis of differently substituted hemiaminals, biscyclopropyl pyrrolidines and 3-vinylated heterocycles were also efficiently achieved and subsequently published. The synthesis of 1,3-dienes and related oligomers were achieved in moderate yields. The control of the oligimerization process was partly controlled, but further work is required for a satisfactory good process, allowing for higher yields and control of oligomer size.
The successful application of acetylene into several Au(I)-catalyzed methodologies showcases the potential of acetylene as a feedstock in a larger range of synthetic transformation than previously realized. It provides inspiration for others to contribute to the area and thus accelerate the rate progress and application into industrially related applications. The progress in understanding the issues in the synthesis of 1,3-dienes presents a good platform for others to continue the work to generate methodologies to rival those currently employed.
This fellowship provided the opportunity for the awarded fellow to develop significantly as a researcher through learning and finetuning his skills with several new techniques (e.g. working with gaseous reagents), in addition to obtain further experience working in a top-class research environment. It will aid him significantly in his future career, whether it is in applying for further fellowships or industrial jobs.
This fellowship provided the opportunity for the awarded fellow to develop significantly as a researcher through learning and finetuning his skills with several new techniques (e.g. working with gaseous reagents), in addition to obtain further experience working in a top-class research environment. It will aid him significantly in his future career, whether it is in applying for further fellowships or industrial jobs.