A Ligand Exchange Process for the Diversification of Palladium Oxidative Addition Complexes

Palladium oxidative addition complexes (OACs) have recently emerged as useful tools to enable challenging bond connections. However, each OAC can only be formed with one dative ligand at a time. As no one ligand is optimal for every cross-coupling reaction, we herein disclose a ligand exchange protocol for the preparation of a series of OACs bearing a variety of ancillary ligands from one common complex. These complexes were further applied to cross-coupling transformations

An Expedited Phenotypic Approach Towards Organic Reaction Generality

Reaction generality is crucial in determining the overall impact and usefulness of organic synthetic methods. In contrast, contemporary generalization processes seem unable to meet the growing demand for robust methodology. We sought to develop an accelerated approach towards achieving generality, inspired by phenotypic screening, that rapidly expands the scope and utility of synthetic methods. This approach was validated by example of the metallaphotoredox decarboxylative arylation, resulting in the discovery of a novel additive that overcomes many lingering limitations of this method and has significant mechanistic implications for nickel-catalyzed cross couplings in general

Secondary modification of oxidatively-modified proline N-termini for the construction of complex bioconjugates

A convenient two-step method is reported for the ligation of alkoxyamine- or hydrazine-bearing cargo to proline N-termini. Using this approach, bifunctional proline N-terminal bioconjugates are constructed and proline N-terminal proteins are immobilized