Harnessing the Reactivity of Acceptor-Acceptor Diazo-Derived Metal Carbenes

With the support of the Chemical Synthesis Program in the Division of Chemistry, Stefan France of Georgia Tech is studying the properties of an important class of synthetic building blocks called acceptor-acceptor carbenes to determine how to tune their reactivity to achieve predictable and controllable new bond connections for the synthesis of value-added compounds. While other types of carbenes with greater electron-density and stability have been carefully studied with a variety of catalysts to support many elegant syntheses, acceptor-acceptor carbenes have lagged behind.

Dr. France and his research team are using a combined experimental and computational approach to address this limitation by compiling fundamental data to understand how to control and predict the reactivity of acceptor-acceptor carbenes in synthetic processes. Different catalysts are also being investigated to achieve different reactivity patterns from the same carbene building blocks.

These studies are helping to improve the synthesis and preparation of fine chemicals and pharmaceuticals by examining a long-standing problem in this area of synthetic chemistry. Simultaneously, these activities are providing interdisciplinary training for a diverse group of graduate and undergraduate students at Georgia Tech and Clark Atlanta University (an HBCU) through a computational collaboration with Dr.

Seyhan Salman. Dr. France is also participating in a program to assist graduate students with professional development and is committed to addressing diversity issues through participation in a variety of campus initiatives to improve recruiting and hiring, as well as student retention.

Acceptor-acceptor metal carbenes have been underutilized in intermolecular C-H functionalization chemistry due to a lack of understanding of their reactivity and stability properties. Stefan France and his research group at Georgia Tech are combining experimental approaches, and collaborative computational efforts in collaboration with Seyhan Salman at Clark Atlanta University, to understand, parametrize, and predict substrate- and catalyst-control for acceptor-acceptor carbene C(sp3)-H insertion.

In addition, Dr. France and his research team are exploring new divergent reactivity patterns of acceptor-acceptor carbenes. This project will serve as a launching pad into new chemical space and for developing enabling technologies to improve access to desirable target molecules.

These activities also will provide training to both graduate and undergraduate students on the interplay between computational and experimental organic chemistry of relevance to catalytic organometallic synthesis.

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.