Synthesis of enantiomerically enriched 4,5-disubstituted N-aminoimidazol-2-one (Nai) peptide turn mimics

N-Aminoimidazolone (Nai) peptide mimics were synthesized with minimal epimerization by base-promoted 5-endo-dig cyclization of aza-propargylglycine dipeptide acids and hydrazides followed by olefin migration. 5-Position functionalization using Mannich amino methylation and Vilsmeier–Haack formylation has given access to a set of restrained side chain analogs of Asp, Dab, and Hse residues for mimicry of turn form and function.

Dual-Function, Light Switchable Cobalt Catalysis via Active Site Metamorphosis

<p></p><p></p><p>Switchable catalysis offers opportunities to control the rate or selectivity of a reaction <i>via</i> a stimulus such as pH or light. However, few examples of switchable catalytic systems that can facilitate multiple processes exist. Here we report a rare example of such dual-functional, switchable catalysis. Featuring an easily prepared, bench-stable cobalt(I) hydride complex in conjunction with pinacolborane, we can completely alter the reaction outcome between two widely employed transformations – olefin migration and hydroboration – with visible light as the sole trigger. This dichotomy arises from ligand photodissociation which leads to metamorphosis of the active catalytic site, resulting in divergent mechanistic pathways.</p><p></p><p></p>

Dual-Function, Light Switchable Cobalt Catalysis via Active Site Metamorphosis

<p></p><p></p><p>Switchable catalysis offers opportunities to control the rate or selectivity of a reaction <i>via</i> a stimulus such as pH or light. However, few examples of switchable catalytic systems that can facilitate multiple processes exist. Here we report a rare example of such dual-functional, switchable catalysis. Featuring an easily prepared, bench-stable cobalt(I) hydride complex in conjunction with pinacolborane, we can completely alter the reaction outcome between two widely employed transformations – olefin migration and hydroboration – with visible light as the sole trigger. This dichotomy arises from ligand photodissociation which leads to metamorphosis of the active catalytic site, resulting in divergent mechanistic pathways.</p><p></p><p></p>