S-Trifluoromethyl Sulfoximine as a Directing Group in Ortho-Lithiation Reaction toward Structural Complexity

Abstract

The first use of the NH S-trifluoromethyl sulfoximine as an ortho directing group is described for the functionalization of the aryl group bonded to the sulfur atom. Various electrophiles (halogen, carbon, oxygen, sulfur, boron, etc.) are introduced on the aromatic ring. Cyclic S-trifluoromethyl sulfoximines are synthesized either with properly chosen electrophiles or by structural adjustment of o-azido sulfoximines. Fluorinated analogues of prazosin are also prepared.

Merging hypervalent iodine and sulfoximine chemistry: a new electrophilic trifluoromethylation reagent

“…Thus, ortho-lithiation followed by quenching with excess iodine gave the iodoarene 5 in excellent yields on a 15 g scale. 18 In a more recent report, sulfoximine 8 could be accessed via a one-pot protocol starting from commercially available phenyl triuoromethyl sulde, using phenyliodine diacetate and ammonium carbamate followed by acid hydrolysis. Application of this method gives compound 5 in two steps as opposed to three, however large scale synthesis via this route has not yet been established.…”

Synthesis of S‐Trifluoromethyl S‐Arylsulfoximine Thioglycosides through Pd‐Catalyzed Migita Cross‐Coupling

“…To reach our synthetic goal, we planned an approach merging the knowledge of both of our research groups: in the chemistry of S‐trifluoromethyl sulfoximine and in the development of strategies devoted to the reactivity of thiosugars under transition metal‐catalysis including Pd‐catalyzed Migita cross‐coupling. The synthesis of o ‐iodo S‐aryl S‐trifluoromethylsulfoximine and the subsequent selective functionalization of the ortho position, in the presence of the free NH sulfoximine was recently carried out . Another interest of the present study would rely on the chiral pool offered by the thiosugars derivatives.…”

One‐Pot Synthesis of Aryl‐ and Alkyl S‐Perfluoroalkylated NH‐Sulfoximines from Sulfides

“…Fluorinated sulfoximines can furthermore act as nucleophiles as performed by Hu, or radical transfer agents . They are also employed as ortho ‐directing groups, building blocks for liquid crystals and as powerful electron‐withdrawing entities . However, the principal drawback to their development is still the lack of general preparation methods.…”