Molecular Iodine Catalyzed Cross-Dehydrogenative Coupling Reaction between Two sp³ C–H Bonds Using Hydrogen Peroxide

Abstract

A useful method for molecular iodine catalyzed oxidative C-C bond formation between tertiary amines and a carbon nucleophile using hydrogen peroxide as the terminal oxidant is reported. This is the first report of a molecular iodine catalyzed cross-dehydrogenative coupling (CDC) reaction between two sp(3) C-H bonds.

CBr4‐Mediated Cross‐Dehydrogenative Coupling Reaction of Amines

“…Interestingly,e thyl 6-methyl-4-phenylquinoline-2carboxylate (3aa)w as produced in 55 %y ield when 1.0 equivalent of CBr 4 was used under air atmosphere (Table 1, entry 5). In addition, both increasinga nd decreasingt he temperature resulted in lower yields (Table 1, entries [11][12][13]. We believe the reasoni st hat the formation of the side product ethyl 2-oxo-2-(p-tolylamino)acetate [7] from self-oxidation can be avoided under thesed ecreasedo xygen concentration conditions.…”

“…This reaction relies on the oxidation of the secondary amine substrates to generate reactive imine intermediates. [11][12][13] To the best of our knowledge,n oC Br 4 -mediated CDC reaction of amines has been described yet. [4] As eries of substituted quinolinesw ere synthesized by using FeCl 3 as the catalyst and a2 ,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) oxoammonium salt as the oxidant.…”

“…[10] Herein, we describe an ovel, metalfree CBr 4 -mediated dehydrogenative Povarov/aromatization tandem reaction of glycine derivatives with alkenes. [11][12][13] To the best of our knowledge,n oC Br 4 -mediated CDC reaction of amines has been described yet. [11][12][13] To the best of our knowledge,n oC Br 4 -mediated CDC reaction of amines has been described yet.…”

“…First, the sp 3 -sp 2 CÀHc oupling between N-aryl tetrahydroisoquinolines and indoles wass uccessfully performed. [12] The combination of N-aryl tetrahydroisoquinolines and phosphites could also give the corresponding CÀP coupling products (Table 3, D). The coupling reaction between two sp 3 CÀHb onds is av ery attractive but challenging area.…”

Metal-free one-pot synthesis of quinoline-2,4-carboxylates via a molecular iodine-catalyzed three-component reaction of arylamines, ethyl glyoxylate, and α-ketoesters

“…Molecular iodine has attracted considerable attention in modern synthetic chemistry due to its charming advantages of cheapness, nontoxicity, water-tolerance and operation simplicity [24][25][26][27][28]. The mild Lewis acidity associated with iodine enhanced its usage in organic synthesis to realize various organic transformations [29][30][31][32][33][34].…”