Sulfoximines with α‐Ketoester Functionalities at Nitrogen from Cyanoacetates and Air

Abstract

Sulfoximines with nitrogen‐bound α‐ketoester units are efficiently prepared by an operationally simple one‐pot reaction sequence in air starting from methoxy(mesyloxy)iodobenzene, NH‐sulfoximines, and cyanoacetates. Key of the process is the in‐situ formation of hypervalent iodine reagents, which serve as electrophilic sulfoximidoyl sources.magnified image

Reactivity of Hypervalent Iodine(III) Reagents Bearing Transferable N‐Based Groups

“…The synthesis of sulfoximines with nitrogen-bound αketoester units 133 via a one-pot reaction under air was reported by Bolm and co-workers [84] in situ generation of hypervalent iodine reagents, as the electrophilic sulfoximidoyl source, was crucial for this transformation. After testing different hypervalent iodine reagents, solvents and bases, the optimal conditions for the formation of product 133, involved 2 equivalents of in situ generated iodine(III) reagent, a tert-butyl cyanoacetate nucleophile 132 and 2 equivalents of Na 2 HPO 4 .…”

“…The synthesis of sulfoximines with nitrogen‐bound α‐ketoester units 133 via a one‐pot reaction under air was reported by Bolm and co‐workers [84] (Scheme 70). Reaction of tert ‐butyl cyanoacetate 132 , and iodine(III) reagent 131 with NH ‐sulfoximine 117 , led to the formation of product 133 .…”

Synthesis and Transformations of NH‐Sulfoximines

“…Bolm reported recently the synthesis of sulfoximines bearing a α‐ketoester functionality at the nitrogen atom. [111] The strategy involved a one‐pot reaction of NH‐sulfoximines and methoxy(mesyloxy)iodobenzene to afford hypervalent iodine reagents that underwent reaction with cyanoacetates, furnishing the desired products 39 in good yields (Scheme 41 , a). The scope of the reaction was thoroughly explored by structural variation at both sulfoximines and cyanoacetates.…”

One-Pot Synthesis of N-Iodo Sulfoximines from Sulfides

“…The increasing interest in sulfoximines − in drug discovery, − medicine, − and agrochemistry , has led to a rapidly growing number of publications − in these and other research areas . These compounds are of great importance as ligands, auxiliaries, and catalysts, e.g., in asymmetric synthesis and catalysis. , Recently, a large number of reports on their synthesis and transformations have appeared in the literature, − including halo- and chalcogenations.…”