Hypervalent Iodine

Transfer of Electrophilic NH Using Convenient Sources of Ammonia: Direct Synthesis of NH Sulfoximines from Sulfoxides

“…In Scheme 4, two possible pathways are proposed and involve the intermediates 3 and 4.W ith the involvement of 3,the formation of the sulfoximine may occur by either direct attack of the sulfoxide at the nitrogen atom, with displacement of iodobenzene, [33,36] or attack at the iodine center, and as ubsequent reductive elimination sequence leading to the sulfoximine. [37] In the case of the 4,adirect nucleophilic attack of the sulfur atom at the electrophilic nitrogen atom would lead directly to 2,a ccording to NMR and MS data. In both pathways,t he nucleophilicity of the sulfoxide is therefore important, thus explaining the reduced reactivity with very electron-poor sulfoxides.…”

Recent discoveries on the structure of iodine(iii) reagents and their use in cross-nucleophile coupling

“…This type of reaction can be called “cross-nucleophile coupling” (in analogy to the “cross-electrophile coupling” in metal catalysis). 38 The coupling is accompanied by the formal loss of two protons or equivalent electrofuges ( e.g. TMS + , t Bu + ).…”

“…Reactions which follow a redox umpolung approach (Scheme 1d) can be termed "cross-nucleophile couplings" in analogy to the term "cross-electrophile couplings" which refers on the use of two electrophilic species in combination with a reductant. 38 compared to the lighter halogen elements. It is the heaviest non-metallic element with stable isotopes.…”

Hypervalent Bromine(III) Compounds: Synthesis, Applications, Prospects

“…The reactivity pattern of hypervalent iodine is somewhat discretely similar to the heavy transition metals and, as such, they are typically preferred as a less toxic alternative. The diverse nature of these reactions includes oxidative couplings, 8 halogenations, 9 arylations, 10 oxidative rearrangements, 11 trifluoromethylations 12 and C-H functionalizations. 13 Their hypervalent bromine analogues can feature superior reactivity owing to their higher nucleofugality, ionization potential and stronger electrophilicity.…”