Development of Catalytic Enantioselective Intermolecular Diene Hydrofunctionalization Reactions

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The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Steven Malcolmson. Professor Malcolmson is a faculty member in the Department of Chemistry at Duke University. The development of new chemical reactions is critical to continued progress within a number of vital technologies, including materials, agriculture, and pharmaceuticals. The needs for the development of synthetic methods include the use of cheap and abundant starting materials while generating minimal chemical waste. One reaction of interest, called a catalytic hydrofunctionalization, adds new abilities to change to readily available molecules. Hydrofunctionalization reactions are currently limited in terms of the types of molecules that can be used and the speed and selectivity of the overall process. To address these limitations, the Malcolmson laboratory is developing a number of new hydrofunctionalization reactions that form carbon-carbon and carbon-nitrogen bonds. The reactions take advantage of commercially available reagents and easily accessed starting materials, and they incorporate all of the atoms from all reagents into the products (atom economy) while using minimal solvent. As such, the reactions generate very little chemical waste. The products generated from the reactions are valuable in that they can serve as synthetic building blocks for use in the fine chemical, agrochemistry, and medicinal chemistry industries. In addition to this work, Dr. Malcolmson and his team are developing a series of short online videos to educate the public and undergraduate and graduate students about how the development of catalytic reactions has shaped the modern world through industrial applications. This effort increases public scientific literacy and fosters an interest in science among precollege and college students while also broadening graduate education, thereby helping to train the next generation of scientists.With funding from the Chemical Synthesis Program of the Chemistry Division, the Malcolmson laboratory at Duke University is developing a number of catalytic site- and enantioselective hydroamination and hydroalkylation reactions of acyclic 1,3-dienes, including challenging internal dienes. Palladium-based catalysts with chiral chelating P,N-ligands allow for efficient and enantioselective reactions of cheap, abundant, and commercially available amines and beta-dicarbonyl pronucleophiles at room temperature within short reaction times. Hydrofunctionalization of dienes offers an expedient and 100% atom economical way to construct compounds with allylic stereogenic centers, valuable building blocks for assembling fine chemicals, agrochemicals, and pharmaceuticals. The high-value products garnered under this project are not easily prepared through competing technologies such as allylic substitution. The methods development outlined in this application along with the accompanying mechanistic investigations may begin to address long-standing challenges in enantioselective hydrofunctionalization technologies and lay the groundwork for related future studies. The educational outreach focuses on increasing public understanding and appreciation for catalysis via production and distribution of a collection of short videos, relating how synthetic catalytic chemistry has shaped the modern world. These videos are available on YouTube.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.