Sulfoximines have recently emerged as interesting motifs for both medicinal and synthetic chemists.

Aryl thiols can be selectively converted to sulfonimidates or sulfonamides with three new S-X connections being made selectively in one pot. Using hypervalent iodine reagents in the presence of ammonium carbamate, NH- and O-groups are transferred under mild and practical conditions. Reducing the loading of ammonium carbamate changed the product distribution, converting the sulfonimidate to the sulfonamide. Studies into the possible intermediate species are presented, suggesting that multiple pathways may be possible via sulfinate esters, or related intermediates, with each species forming the same products.

Scheme 2. Rhodium-catalyzed imination of sulfoxides and deprotection reaction. Scheme 3. Electrochemical imination of sulfoxides. Scheme 4. Direct Rh-catalyzed synthesis of NH-sulfoximines from sulfoxides.

The not so elusive carbenoid fluoroiodomethyllithium disclosed its electrophilic nature in an unprecedented direct and stereoselective fluorocyclopropanation of allylic alcohols.

An expeditious, high-yielding synthesis of rare α-fluoroepoxides and α-fluoroaziridines through the addition of the unkown fluoroiodomethyllithium (LiCHIF)formed via deprotonation the commercially available fluoroiodomethane with a lithium amide baseto carbonyl-like compounds is documented. The ring-closure reactions, leading to α-fluorinated three-membered heterocycles, rely on the diversely reactive C–I and C–F bonds. Excellent chemoselectivity was observed in the presence of highly sensitive functionalitiesaldehyde, ketone, nitrile, alkenewhich remained untouched during the homologation sequence.

Sulfonimidamides are intriguing new motifs for medicinal and agrochemistry, and provide attractive bioisosteres for sulfonamides. However, there remain few operationally simple methods for their preparation. Here, the synthesis of NH‐sulfonimidamides is achieved directly from sulfenamides, themselves readily formed in one step from amines and disulfides. A highly chemoselective and one‐pot NH and O transfer is developed, mediated by PhIO in iPrOH, using ammonium carbamate as the NH source, and in the presence of 1 equivalent of acetic acid. A wide range of functional groups are tolerated under the developed reaction conditions, which also enables the functionalization of the antidepressants desipramine and fluoxetine and the preparation of an aza analogue of the drug probenecid. The reaction is shown to proceed via different and concurrent mechanistic pathways, including the formation of novel S≡N sulfanenitrile species as intermediates. Several alkoxy‐amino‐λ6‐sulfanenitriles are prepared with different alcohols, and shown to be alkylating agents to a range of nucleophiles.

The external quenching method based on flow microreactors allows the generation and use of short‐lived fluoro‐substituted methyllithium reagents, such as fluoromethyllithium, fluoroiodomethyllithium, and fluoroiodostannylmethyllithium. Highly chemoselective reactions have been developed, opening new opportunities in the synthesis of fluorinated molecules using fluorinated organometallics.

NH-sulfoximines are emerging as useful and important targets in drug discovery and synthetic organic chemistry. We report herein the development of an efficient, convenient, and sustainable continuous-flow strategy, for the direct, straightforward preparation of NH-sulfoximines by using sulfides or sulfoxides as suitable starting material. The flow process