A palladium(II) catalyst, in the presence of Selectfluor, enables the efficient and chemoselective transformation of primary amides into nitriles. The amides can be attached to aromatic rings, heteroaromatic rings, or aliphatic side chains, and the reactions tolerate steric bulk and electronic modification. Dehydration of a peptaibol containing three glutamine groups afforded structure–activity relationships for each glutamine residue. Thus, this dehydration can act similarly to an alanine scan for glutamines via synthetic mutation.

Phenylcyanocarbene was generated by the reaction of azide with a hypervalent iodonium alkynyl triflate and reacted in situ with 21 different carbocyclic and heterocyclic aromatic compounds. These reactions led to more complex products that frequently underwent subsequent rearrangements. The reactivity was further explored in a mechanistic study to ascertain the chemoselectivity and stereospecificity.

We herein report the development of a protocol for the olefination of oximes, resulting in cyclic alkene products. Our approach relies on the in situ formation of Ru alkylidenes from [RuCl2(p-cymene)]2 and 3,3-diphenylcyclopropene as carbene precursors and gives rise to the desired functionalized alkenes in yields up to 58%. Compared to our previously reported strategy for oxime olefination, it foregoes the use of commercially available Ru alkylidenes, including Hoveyda–Grubbs 2. This is desirable concerning the overall costs of this transformation and also provides important mechanistic insights into the development of future catalytic variants of this reaction as the alkylidenes required for efficient olefination can be generated in situ.