Homogeneous Organocalcium and Organolanthanide Catalysis for the Formation of C–N Bonds and Selective C–O Bond Cleavage

Dicken, Rachel Dowrey

doi:https://doi.org/10.21985/n2-h1ja-nn74

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Homogeneous Organocalcium and Organolanthanide Catalysis for the Formation of C–N Bonds and Selective C–O Bond Cleavage

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Among the most valuable applications of organometallic chemistry is its implementation in the field of catalysis. Many industrial processes rely heavily on catalysis, employing organometallic complexes in the production of commodity chemicals, fine chemicals, materials, and even in the discovery and development of pharmaceuticals. Through decades of intense study, homogeneous catalysis using the precious metals has allowed for tremendous advances in modern synthesis by providing access to robust, reliable, and often predictable chemistry. However, given that there are also a number of limitations associated with the use of precious metals (i.e., Pt, Pd, Ir, Rh, Ru, Au, and Ag) including high cost and environmental impact, and limited availability, the use of more sustainable metal catalysts and the new reactivity and selectivity that they may offer has gained increasing attention.Relative to the late transition metals, the catalytic chemistry of the more sustainable alkaline earth and rare earth elements is less well understood, as their reactivity is fundamentally different than that of the transition metals. The work described herein details the investigation of two catalysts which make use of the abundant and environmentally benign metals calcium and lanthanum. The first project involves the development of a direct enantioselective conjugate addition of unprotected alkyl amines to maleimides using a chiral calcium(II)-phosphate complex to generate chiral aminosuccinimides. The second project presents a chemoselective organolanthanide amide-catalyzed deoxygenative reduction of amides with pinacolborane to provide access to a diverse set of amines. Investigation into the kinetics, thermodynamics, and mechanism of the latter is also described.

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