The direct installation of electron-deficient nitrogen functionalities to complex molecules is a valuable goal in the production of pharmaceuticals and advanced materials. Our research group has recently developed a novel method of N-incorporation that utilizes a light-promoted, N-centered radical (NCR) pathway involving an intermediate N,N-diiodosulfonamide reactive species. The N,N-diiodosulfonamide species, which can produce two distinct N-centered radicals due to relatively weak N-I bonds, are produced in situ from an iminoiodinane reagent (PhI=NZ) and I2. In an effort to gain mechanistic insight to the reactive species, density functional calculations of N-I bond dissociation energies for a range of different N,N-dihalosulfonamides were performed using a B3LYP 6-311++G(2df,2p) method. The trends observed from this study will be presented along with experimental results from the screening of a series of N,N-diiodosulfonamides with varying electronic properties to produce N-sulfonylimines from aldehydes.

Calculation of bond dissociation energies of electronically different N,N-dihalogenated sulfonamides

255th National Meeting (2018)

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