TunDrivChem
Quantum Tunneling Driving C-H Bond Activation Reactions via Nitrenes
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Project: Quantum Tunneling Driving C-H Bond Activation Reactions via Nitrenes
Principal Investigator: Cláudio M. Nunes
Host Institution: University of Coimbra
Consultants: Peter R. Schreiner and Artur Mardyukov (DE); Pablo Ballester (ES); Robert McMahon (USA)
Funding [50 k € ]: 2023.11222.PEX, funded by National Funds via the Portuguese Foundation for Science and Technology (FCT)
Summary
Summary
An overarching goal of our group is to conduct leading research that brings QMT (Quantum Mechanical Tunneling) reactivity paradigms into organic synthesis laboratories. This project intends to inaugurate such a research program by establishing proof-of-concept synthetic strategies based on QMT driving C−H bond activation reaction via nitrenes. The research plan is supported by our pioneering discoveries on QMT in nitrene chemistry. Investigations will transition research from cryogenic matrices to cold solution conditions and then to organic synthesis laboratories. This will include advanced investigations on the fundamentals of QMT reactivity and their application to molecular design on a preparative scale. The realization of synthetic strategies driven by QMT have the potencial to create unique opportunities for discovering new and efficient transformations, which are crucial to render, in a sustainable way, the future generation of molecules.
Chronology and Milestones
07.25 Our new work investigating tunneling through high-energy barriers, using hydrogen tunneling in thiobenzamide as a case study, has just been published in J. Org. Chem. (link).
We present here the intriguing case of thiobenzamide thiol - thione QMT H-shift tautomerization, with a half-life of ∼ 180 h (Ar matrix at 10 and 20 K), despite a computed high-energy barrier of ∼25 kcal/mol. Computed CVT/SCT rate constants closely reproduce the experimental data. Remarkably, computations extended to higher temperatures indicate that even at 300 K the H-shift tautomerization is entirely governed by QMT (>99.9%). The predicted half-life at 300 K is ∼1 min whereas at 200 K is ~200 min, making it amenable to investigation in cold solutions and with stationary spectroscopy.
These findings reveal an exceptional reaction model for exploring QMT-governed reactivity under solution conditions and for providing new insights into harnessing QMT in molecular design.
5.25 We have just closed a position for a MSc Researcher. Sofia Braz was selected and will be working on the TunDrivChem project in the next 9 months
2.25 Our TunDrivChem project have started!
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