ChemInform Abstract: Umpolung Amide Synthesis Using Substoichiometric N‐Iodosuccinimide (NIS) and Oxygen as a Terminal Oxidant.

Abstract

Umpolung Amide Synthesis Using Substoichiometric N-Iodosuccinimide (NIS) and Oxygen as a Terminal Oxidant. -Reaction of -bromo-nitroalkanes with amines using O 2/NIS as oxidative catalytic system gives the respective amides with high stereoselectivity (dr >20:1). Amino acids as well as peptides can also be used as amine source. -(SCHWIETER, K. E.; SHEN, B.; SHACKLEFORD, J. P.; LEIGHTY, M. W.; JOHNSTON*, J. N.; Org. Lett. 16 (2014) 18, 4714-4717, http://dx.doi.org/10.1021/ol502089v ; Dep. Chem., Vanderbilt Univ., Nashville, TN 37235, USA; Eng.) -M. Tismer 10-056

Nonclassical Routes for Amide Bond Formation

“…On the basis of these mechanistic studies, the the source of X + (bromonium vs iodonium) in the halamine synthesis was next questioned. 359 Control experiments brought the Johnston's group to develop an aerobic and catalytic version of the reaction where NIS can be used in 5 mol % in the presence of oxygen as the terminal oxidant (Scheme 135). It should be emphasized that yields compare favorably with those obtained in the stoichiometric-NIS version of the reaction.…”