The Asymmetric Rh(I)-Catalyzed Pauson–Khand Reaction

Kay M. Brummond / University of Pittsburgh, USA

June 27, 2024, 3 - 4 pm CEST

Online live talk

Introduction

In the fifty years since being discovered, the Pauson–Khand reaction (PKR) has transformed the design and synthesis of ring-fused cyclopentenones – an unsaturated motif of immense value for building complex molecular compounds. Moreover, the PKR is frequently used in natural product synthesis, owing to the predictable and high diastereoselectivity afforded by this cyclocarbonylation reaction. And yet, the scope of the asymmetric PKR remains limited. This presentation will be on the discoveries made in our research group that led to the expansion of the scope of the Rh(I)-catalyzed asymmetric PKR through catalyst-controlled reactivity modes. Moreover, the application of our findings to the synthesis of the medicinally important target thapsigargin will be highlighted.

Kay M. Brummond

is an organic chemist and a Professor of Chemistry at the University of Pittsburgh. She received her BS degree from the University of Nebraska-Lincoln (1985), her PhD in organic chemistry from The Pennsylvania State University (1991), and she performed her postdoctoral studies in organic chemistry at the University of Rochester (1991–1993). Her first faculty appointment was in the Department of Chemistry at West Virginia University in 1993 where she was promoted to Associate Professor with tenure (1999). In 2001, Brummond joined the Department of Chemistry at the University of Pittsburgh as an Associate Professor and was promoted to Professor in 2006. She served as the first female departmental chair in their 160-year history (2014–2017) and as the Associate Dean for Faculty in the Dietrich School of Arts and Sciences (2017–2023). She and her coworkers have published 92 journal articles, reviews, and book chapters. Brummond has delivered 190 presentations as an invited speaker for departmental colloquia and seminars (135) and as a plenary lecturer for symposia and conferences (55).

 

Brummond’s research program uses mechanistic insight to discover and develop new chemical transformations involving transition metal-catalyzed cyclocarbonylation and carbocyclization reactions of allene-ynes and enynes and thermal cycloaddition reactions of arenes and heteroarenes; her group demonstrates the utility of these transformations by designing and synthesizing complex molecular compounds having function crucial to pharmaceutical and organic material ecosystems. Brummond’s excellence in organic chemistry has been recognized as the recipient of the 2021 National ACS Award for Encouraging Women into the Chemical Sciences, where she was identified as a “pathfinder, an agent of change, and mentor to women at all stages of their careers in the Chemical Sciences.” In 2021, she was elected as an American Association for the Advancement of Science Fellow for her contributions in organic chemistry to “regulate chemical reactivity of cycloaddition reactions informed by a mechanistic understanding.” In 2021, she was elected to the Board of Directors for Organic Syntheses, a publication of reliable methods for the preparation of organic compounds, which she previously served on the Board of Editors (2006–2014) and edited Organic Synthesis, Volume 91. In 2018, she received the Chancellor’s Distinguished Public Service Award for her many efforts at the University of Pittsburgh and within the chemical community, such as creating the University of Pittsburgh Summer Undergraduate Research Fellowship program, which offers research opportunities to students from underrepresented groups majoring in chemistry, and for serving as the Executive Director for the 45th National Organic Chemistry Symposium (2017) having the most diverse line-up of speakers in the history of the meeting at that time.