Process for Acceptorless Dehydrogenation of Alkanes Through Dual Catalysis

Dual Base Metal Catalysis for Alkene and Hydrogen Production via Acceptorless and Selective Dehydrogenation of Alkanes

Princeton Docket # 15-3117

Researchers in the Department of Chemistry at Princeton University have developed a new catalyst combination, comprising of a tungsten-based polyoxometalate and cobaloxime, in order to dehydrogenate alkanes to produce molecular hydrogen and alkenes, important petrochemical feedstocks.  Saturated organic compounds may be dehydrogenated through the synergistic function of two base metal catalysts.  Current methods for the acceptorless dehydrogenation of unactivated substrates, such as alkanes, rely on noble metal catalysts and require forcing conditions to drive the reaction or, in the case of tandem photoredox-noble metal catalysis, result in complex product mixtures.  A combination of an excited state catalyst and a ground state catalyst successively removes hydrogen atoms from the substrate, resulting in selective dehydrogenation with evolution of molecular hydrogen.  Neither catalyst contains a noble metal, which enhances reaction selectivity and reduces cost.  The reaction can be carried out at room temperature using solar irradiation.

Applications:   

·         Production of alkenes from alkanes for commodity petrochemicals

·         Production of hydrogen from alkanes, as well as other unactivated and activated substrates

·         Selective dehydrogenation of complex molecules

Advantages: 

·         Novel catalyst combination of tungsten polyoxometalates (POMs) and cobaloximes

·         Catalysts easy to synthesize or commercially available

·         Inexpensive and abundant feedstocks

·         No noble metals

·         Mild reaction conditions of room temperature and near-UV irradiation

·         Substrate compatibility

·         Highly selective dehydrogenative olefination

Key Words

Catalysis, alkane, alkene, olefin, hydrogen, petrochemical, selective dehydrogenation, tungsten polyoxometalate, cobaloxime, solar irradiation, activated substrate, base metal

Related Publications

West, J.G. and Sorensen, E.J.  Acceptorless Dehydrogenation of Alkanes through Cooperative Base Metal Catalysis, submitted, (2015).

Inventors

Erik J. Sorensen, Ph.D. and Julian G. West

Faculty Inventor

Erik J. Sorensen, Arthur Allan Patchett Professor in Organic Chemistry

The Sorensen laboratory is interested in the field of complex chemical synthesis, questions about the structural origins of architecturally unique natural products, and evaluating hypotheses about the chemical basis of the biological activities of natural products and non-natural molecules.  His research aims to increase the capabilities of organic synthesis through the development of powerful reactions and strategies.

Professor Sorensen was born and raised in upstate New York and received his B. A. degree in Chemistry from Syracuse University, where he performed undergraduate research with Professor Roger Hahn.  In 1989, he began his graduate studies in chemical synthesis at the University of California, San Diego.  Under the direction of Professor K. C. Nicolaou, he synthesized a novel family of DNA cleaving, 10-membered ring enediynes, contributed to a laboratory synthesis of the cancer drug taxol and co-authored a book titled Classics in Total Synthesis, and obtained his Ph. D. degree in 1995.  From 1995-1997, he was a National Science Foundation postdoctoral fellow in the laboratory of Professor Samuel Danishefsky at The Memorial Sloan-Kettering Cancer Center in New York, where he contributed to total syntheses of the epothilone class of antitumor agents.  In 1997, he started his independent career at The Scripps Research Institute and became an Associate Professor with tenure in 2001.  In 2003, he moved his research group to Princeton University, where he is the Arthur Allan Patchett Professor in Organic Chemistry.

For his achievements in chemical research and education, Professor Sorensen has received a Beckman Young Investigator Award, a Camille Dreyfus Teacher-Scholar Award, the AstraZeneca Award for Excellence in Chemistry, the Lilly Grantee Award, the Pfizer Global Research Award for Excellence in Organic Chemistry, and the Bristol-Myers Squibb Unrestricted Grant in Synthetic Organic Chemistry.  In 2001, Professor Sorensen was a Woodward Scholar at Harvard University.  In 2007, he was the Givaudan/Karrer Distinguished Visiting Professor at the University of Zürich.  In 2009, he received the Arthur C. Cope Scholar Award from the American Chemical Society.

Intellectual Property Status

Patent applications are pending.  Princeton is seeking industrial collaborators for further development and commercialization of this technology.

Contact

Laurie Tzodikov
Princeton University Office of Technology Licensing • (609) 258-7256• tzodikov@princeton.edu

Sarah Johnson

Princeton University Office of Technology Licensing • sajohnso@princeton.edu