Molybdenum-Mediated Reductive Hydroamination of Vinylcyclopropanes with Nitroarenes: Synthesis of Homoallylamines

Abstract

A molybdenum-mediated reductive hydroamination of vinylcyclopropanes with nitroarenes has been developed. A broad range of substituted homoallylamines were prepared in good to excellent yields from readily available starting materials. No noble metal catalysts were used in this reaction, and Mo(CO) 6 acted as both catalyst and reductant. This protocol provides an effective method for the selective synthesis of substituted homoallylamines from easily available nitroarenes.

Recent progress in the synthesis of N-substituted arylamines by reductive cross-coupling of nitroarenes

“…In 2023, the Peng group developed a molybdenum-mediated reductive amination reaction of vinylcyclopropane with nitroarenes to prepare a wide range of homoallylamines (Scheme 35). 59 Notably, no noble-metal catalysts are used; instead, Mo(CO) 6 acts as both catalyst and reducing agent. This method is a good alternative to transition metal-catalyzed construction of homoallylamines.…”

Halogen Promoted Desulfurative Cleavage of Cyclopropylmethyl Thioethers and Amination of the Formed Cyclopropylcarbinyl Cations

“…The development of CÀ N bond-forming reactions is a research field with the utmost impact on Organic synthesis due to the ubiquitous presence of nitrogenated compounds in drugs and material science building blocks. [1] For example, although classical approaches for the synthesis of homoallylic amines are commonly based on the addition of allyl organometallics to imines, [2] other alternative strategies involving CÀ N bondforming [3] demonstrated to be highly versatile for the formation of these compounds like hydroamination reactions, [4] alkylation, reductive amination, [5] electrochemical processes, [6] or photoredox couplings. [7] In this context, cyclopropane ring-opening reactions [8] were demonstrated to be valuable methods for accessing homoallyl amines.…”