Iodine Anion Catalyzed Cross-Dehydrogenative Aromatization for Access to Aromatic Amines

Abstract

A highly efficient iodine anion catalyzed cross-dehydrogenative aromatization of cyclohexenones with amines has been developed under metal-free conditions, which affords aromatic amines in good to excellent yields with a broad substrate scope. Meanwhile, this reaction provides a new method for the construction of C­(sp2)–N bonds and also a new strategy for slow generation of oxidants or electrophiles via in situ dehalogenation. Moreover, this protocol affords a rapid and concise approach to chiral NOBIN derivatives.

Reductive thiolation and oxidative dehydroaromatization of cyclohexanones with primary amines and sodium sulfinates to access o-sulfanylanilines

“…(2) The conversion of cyclohexanones to 1,2-aminothiolated arenes requires multiple elementary reactions, including reductive ortho -thiolation of cyclohexanones, condensation with primary amines and dehydroaromatization, which must be orderly and compatible. (3) Inevitable side reactions, such as 1,2-diamination of cyclohexanones with arylamines, 11 undesirable overthiolation of the resulting product, 12 dehydroaromatizing amination 13 and disproportionate coupling of sodium sulfinates, 14 are extremely complicating issues (Scheme 1B).…”

Aminoselenation and Dehydroaromatization of Cyclohexanones with Anilines and Diselenides

“…Therefore, the choice of a suitable reaction system to avoid the dehydroaromatization of α-seleno cyclohexanones and promote their condensation with anilines is crucial for determining the success of cyclohexanone difunctionalization. Additionally, challenges are inevitably confronted with several side reactions, such as dehydrogenative homocoupling of anilines, dehydroaromatization of cyclic ketones with anilines, overselenation of aminoselenative products with diselenides, para-selenation of anilines with diselenides, and dehydrogenative diamination of cyclohexanones with anilines . It is noteworthy that the current deoxygenative difunctionalization of cyclic ketones not only addresses the frequently encountered region- and chemo-selectivity in arenes chemistry but also provides a conceptual new protocol for the preparation of polyfunctional arenes.…”

Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes

“…However, from the perspective of sustainable chemistry, the above protocols require the use of excessive heavy metal salts (CuX 2 ) or N -halogen compounds as the halogen source. Moreover, we had recently reported an iodine anion-catalyzed cross-dehydrogenative aromatization in which the iodine anion-catalyzed in situ dehalogenation of 1,2-dichloroethane (DCE) was applied as the oxidant . And, our group has had a long-standing interest in the study of the alkynyl-tethered cyclohexadienones .…”