AbstractEarth-abundant metal catalysts are important for future polymer production. Iron is both an earth-abundant and non-critical element and is attracti

Developing asymmetric methodologies using readily available building blocks remains a central challenge in chemical synthesis. Despite advances in asymmetric multicomponent radical cross-couplings, methods that use earth-abundant iron catalysts and nonphosphine ligand platforms remain rare and poorly understood. We report an iron-catalyzed asymmetric radical dicarbofunctionalization of vinyl boronate esters using inexpensive iron salts with chiral bisoxazoline or amide ligands, affording diverse, enantioenriched alkyl boron compounds with high levels of stereoselectivity (up to 99:1 e.r.). Mechanistic investigations combining 80 K 57Fe Mössbauer spectroscopy, single-crystal X-ray analysis, and quantum mechanical calculations reveal a catalytic cycle involving chiral bis- and mono-aryl iron (II) (BOX) species responsible for radical capture and C−C bond formation. This work establishes a distinct mechanistic paradigm for asymmetric radical cross-coupling and provides general design principles for enantioselective catalysis with earth-abundant metals.

A new synthetic approach to accessing a wide range of diphosphinoborane ligands and their coordination behaviour to low-valent nickel centres is described. The synthetic route negates the use of ArBCl2, which are challenging to access, and utilizes ...

For recent publications relevant to the project see: J. Am. Chem. Soc. 2023, 145, 27993; J. Am. Chem. Soc. 2024, 146, 15000; Nat. Commun. 2019, 10, 3330; Chem. Sci. 2024, 15, 3003.

Despite intense interest, the mechanism of iron-catalyzed aryl–aryl cross-coupling remains poorly understood. Combining Mössbauer spectroscopy, kinetics analysis, and DFT computations these studies r...

PhD Project - Combined Synthetic and Computational Understanding of New Heterobimetallic Dimetallocenes at The University of Manchester, listed on FindAPhD.com

Homogeneous catalytic hydroboration represents a valuable strategy for the synthesis of alcohols but reports which employ iron-based catalysts are somewhat limited. Here, the authors report an iron me...

C–H activation is a vital synthetic tool due to its superior atom economy and improved step efficiency making it amendable to late-stage functionalisation. In recent years iron has been gaining tracti...

Please note that job descriptions are not exhaustive, and you may be asked to take on additional duties that align with the key responsibilities ment...

PhD Opportunity – Fully Funded Scholarship in Titanium Catalysis A fully funded PhD scholarship is available to join the Falconer Group at the University of Auckland. This project will focus on titan...

Despite the long-standing importance of iron-silicon bonds as related to catalysis, high-spin Fe(0)-silyl complexes remain a historical synthetic challenge in the field. Herein, we report the first s...

PhD Project - PhD Studentship in C–H Functionalisation Using Polymetallic Complexes at Imperial College London, listed on FindAPhD.com

Previous studies have hinted at the similarities of Mn(II) and Mg alkyl complexes. Advancing this field, here we present a comparative study of tetra(n-butyl) lithium manganate(II) and magnesiate. Com...