Carbon-nitrogen (C−N) bonds are extensively prevalent in pharmaceuticals, agrochemicals, diverse bioactive natural products. An effective strategy for introducing a new C−N bond into a molecule is through transition metal-catalyzed nitrene transfer chemistry. In these reactions, a metal-supported nitrene group/entity can either add across a C=C bond to form an aziridine or insert into a C−H bond to yield the corresponding amine.Extensive work has been carried out with respect to the classic N(CH2CH2NH2)3(TREN) ligand framework by Dr. Richard R. Schrock that has provided motivation to attempt modifications to the ligand scaffold, which would provide weaker equatorial coordination field, as well as would be more supportive of metal-centred atom/group transfer catalysis. There is also indication from previous work that the N(CH2CH2NH2)3 (TREN) framework, along with several metal centres, serves greatly towards isolating intermediates, but not towards viable catalytic processes. In the present work, we have developed cationic first-row transition-metal complexes with tetramethylated guanidinyl arms (TMG3trphen), which are the most promising members among the family of reagents. We have examined a family of bipodal and tripodal catalytic systems that rely on metal reagents, such as copper, to selectively mediate aziridination of styrenes, para-substituted styrenes and many alkyl olefins. We have also carried out catalytic amination reactions on a series of benzylic and allylic substrates. In addition, we have also tried to take advantage of divalent, first-row transition-metal sites (Mn, Fe, and Co) that have been less explored in nitrene transfer chemistry and are certainly more economical and less toxic than the platinum- group elements that have been extensively explored in the field.

Nitrene transfer chemistry mediated via transition metal (M = Cu, Mn, Fe and Co) coordination reagents

ACS Spring Meeting 2021

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