Sulfonylimino Group Transfer Reaction Using Imino-λ3-iodanes with I2 as Catalyst Under Metal-free Conditions

Abstract

A new practical procedure of imination for sulfide has been developed. The treatment of (N-tosylimino)-phenyl-λ3-iodane, PhINTs, with various sulfides in the presence of a catalytic amount of I2 under metal-free conditions affords the corresponding N-tosylsulfilimine compounds with moderate to good yields. This facile transfer procedure of the sulfonylimino group can also be applied to triphenylphosphine to produce the respective iminotriphenylphosphoranes in high yields. According to the reaction mechanism studies, the process of imination from (N-tosylimino)-phenyl-λ3-iodane to sulfide under the conditions may involve radical steps within the reaction mechanism.

Catalytic Chemoselective Sulfimidation with an Electrophilic [CoIII(TAML)]−‐Nitrene Radical Complex**

“…N ‐Haloamides (and derivatives), (in situ prepared) iminoiodinanes, azides, and heterocyclic nitrene precursors have all been used as imidation reagents [1a] . In addition, uncatalyzed sulfimidation and sulfoximidation of S ‐alkyl and S ‐aryl sulfides with in situ formed PhINNs (Ns=nosyl, 4‐(nitrophenyl)sulfonyl) occurs at prolonged heating in MeCN (16 h, 82 °C) [12] and the I 2 ‐catalyzed sulfimidation is also known, producing N ‐tosylsulfimides (tosyl=Ts, 4‐(methylphenyl)sulfonyl) at room temperature [13] . Alternatively, N,O ‐group exchange to form sulfimides from sulfoxides can be achieved with the zwitterionic Burgess reagent ( + NEt 3 SO 2 N − CO 2 R) [14] …”

“…[1a] In addition, uncatalyzed sulfimidationa nd sulfoximidation of S-alkyl and S-aryl sulfides with in situ formed PhINNs (Ns = nosyl, 4-(nitrophenyl)sulfonyl) occurs at prolonged heatingi nM eCN (16 h, 82 8C) [12] and the I 2 -catalyzed sulfimidation is also known, producing N-tosylsulfimides (tosyl = Ts,4 -(methylphenyl)sulfonyl) at room temperature. [13] Alternatively, N,O-group exchange to form sulfimides from sulfoxides can be achieved with the zwitterionic Burgess reagent ( + + NEt 3 SO 2 N À CO 2 R). [14] Surprisingly,c obalt-catalyzed nitrene transfer to sulfur atoms remains largely unexplored.…”

Metal-free C–H Activation over Graphene Oxide toward Direct Syntheses of Structurally Different Amines and Amides in Water

“…First, the reaction conditions were optimized taking benzene 1a as a model substrate with different solvents (Table ). We have chosen GO and iodine to carry out preliminary experimentation for nitrene insertion using PhINTs . The reaction was performed by taking a mixture of I 2 (0.05 mmol), PhINTs (0.5 mmol), GO (20 mg), and benzene (2 mmol) in 5 mL of water and the reaction mixture was stirred at room temperature.…”

Iodonium imides in organic synthesis

“…A practical metal-free procedure for the imidation of sulfides with aryliodonium imides was recently reported. 174 In particular, the reaction of various sulfides 73 with ArINTs 74 in the presence of a catalytic amount of iodine under mild conditions affords the corresponding N-tosylsulfilimines 75 in moderate to good yields (Scheme 27). This facile transfer procedure of sulfonylimino group can also be applied to triphenylphosphine to produce the respective iminotriphenylphosphoranes in high yields.…”