Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ6‐sulfanenitrile Intermediate

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.     

Polymer‐Supported Hypervalent Iodine Reagent Mediated Synthesis of α‐Azidoketones

The reaction of aryl ketones with sodium azide using polymer‐supported bis(trifluoroacetoxyiodo)‐benzene (PSBTI) in the presence of trifluoroacetic acid (TFA) to prepare α‐azidoketones in one‐pot conditions is reported.     

Hypervalent Iodine(III) Mediated Synthesis of 2‐Substituted‐5‐Aryloxazoles

A direct and efficient method for the preparation of 2‐substituted‐5‐aryloxazoles was realized by reaction of aryl methyl ketones with various nitriles in the presence of phenyliodine(III) triflate.     

Total Synthesis of (−)‐Cleistenolide

An efficient and short total synthesis of (?)‐cleistenolide ( 1 ) from D ‐mannitol with an overall yield of 23.6% is described. The chiron approach for the synthesis of (?)‐cleistenolide involves a one‐C‐atom Wittig olefination, a selective allylic triethylsilyl protection, and a Grubbs‐catalyzed ring‐closure‐metathesis (RCM) reaction as the key steps.