Development of a Nickel-Catalyzed N-N Coupling for the Synthesis of Hydrazides.

A nickel-catalyzed N-N cross-coupling for the synthesis of hydrazides is reported. O-Benzoylated hydroxamates were efficiently coupled with a broad range of aryl and aliphatic amines via nickel catalysis to form hydrazides in an up to 81% yield. Experimental evidence implicates the intermediacy of electrophilic Ni-stabilized acyl nitrenoids and the formation of a Ni(I) catalyst via silane-mediated reduction. This report constitutes the first example of an intermolecular N-N coupling compatible with secondary aliphatic amines.

Catalytic rearrangements of onium ylides in aromatic systems.

Onium ylides are reactive intermediates that undergo versatile chemical transformations to give structurally interesting compounds. Rearrangement reactions of onium ylides are of great importance to synthetic organic chemists, as they provide efficient methods for C-C bond formations as well as installation of new stereogenic centers in molecules. Traditionally, onium ylides have been shown to undergo two types of rearrangements, namely, [2,3]- and [1,2]-rearrangements. In recent years, there have been tremendous developments in the field of metal-catalyzed onium ylide rearrangements through catalytic generation of ylide intermediates from diazocompounds. Several examples of selective catalytic onium ylide rearrangements involving sulfonium, oxonium, ammonium, as well as iodonium ylides have been developed over the years especially in allylic and propargylic systems. However, when the π-system that takes part in the rearrangement is part of an aromatic ring, the selectivity for rearrangements of reactive onium ylides is more challenging. In this review, we discuss recent advances in catalyst control of onium ylide rearrangements of aromatic systems.

Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides.

We have developed catalyst-controlled regiodivergent rearrangements of onium-ylides derived from indole substrates. Oxonium ylides formed in situ from substituted indoles selectively undergo [2,3]- and [1,2]-rearrangements in the presence of a rhodium and a copper catalyst, respectively. The combined experimental and density functional theory (DFT) computational studies indicate divergent mechanistic pathways involving a metal-free ylide in the rhodium catalyzed reaction favoring [2,3]-rearrangement, and a metal-coordinated ion-pair in the copper catalyzed [1,2]-rearrangement that recombines in the solvent-cage. The application of our methodology was demonstrated in the first total synthesis of the indole alkaloid (±)-sorazolon B, which enabled the stereochemical reassignment of the natural product. Further functional group transformations of the rearrangement products to generate valuable synthetic intermediates were also demonstrated.