A mild and operationally convenient amino-functionalization of a range of tertiary alkyl halides by reaction with iminoiodinanes (PhI[double bond, length as m-dash]NNs) and I2 has been developed. According to the mechanistic experiments described within, the reaction is speculated to proceed through a light-promoted, N-centered radical pathway involving a N,N-diiodosulfonamide reactive species. This method of direct N-incorporation offers an attractive alternative to the production of α-tertiary amines, a synthetically challenging structural class found in a variety of bioactive molecules.

A general approach for the synthesis of bis(imidazolium) dichloride salts from imidazoles and dichloroalkanes is reported. Typical limitations of this reaction for the formation of methylene-bridged derivatives are addressed herein through the use of an excess CH2Cl2 in the presence of DMSO as a polar cosolvent, significantly improving conversion rates presumably via stabilization of the initial SN2 transition state. The method was also shown to be applicable to the formation of bis(pyridinium) dichloride salts from pyridine derivatives, and to the direct synthesis of metal-bis(NHC) complexes from imidazoles. ASSOCIATED CONTENT Supporting InformationExperimental details and spectroscopic data.

A general approach for the synthesis of bis(imidazolium) dichloride salts from imidazoles and dichloroalkanes is reported. Typical limitations of this reaction for the formation of methylene-bridged derivatives are addressed herein through the use of an excess CH2Cl2 in the presence of DMSO as a polar cosolvent, significantly improving conversion rates presumably via stabilization of the initial SN2 transition state. The method was also shown to be applicable to the formation of bis(pyridinium) dichloride salts from pyridine derivatives, and to the direct synthesis of metal-bis(NHC) complexes from imidazoles.

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